Sol-gel derived porous microcomposite of perfluorinated ion-exchange polymer and metal oxide

ABSTRACT

Porous microcomposites have been prepared from perfluorinated ion-exchange polymer and metal oxides such as silica using the sol-gel process. Such microcomposites possess high surface area and exhibit extremely high catalytic activity.

[0001] This application is a continuation-in-part of application Ser.No. 08/362,063, filed Dec. 22, 1994, which is a continuation-in-part ofapplication Ser. No. 08/180,250, filed Jan. 12, 1994, now abandoned.

FIELD OF THE INVENTION

[0002] This invention relates to porous microcomposites comprisingperfluorinated ion-exchange polymers (PFIEP) containing pendant sulfonicacid groups and/or pendant carboxylic acid groups entrapped within andhighly dispersed throughout a metal oxide network, prepared using asol-gel process. Due to their high surface area and acid functionalitythese microcomposites possess wide utility as improved solid acidcatalysts.

TECHNICAL BACKGROUND

[0003] U.S. Pat. No. 5,252,654 discloses polymeric composites comprisingan interpenetrating network of an organic polymer and an inorganicglassy polymer and a process for making such composites. The disclosedmaterial is nonporous, and the use of perfluorinated ion-exchangepolymers (PFIEP) containing pendant sulfonic acid groups or pendantcarboxylic acid groups is not disclosed.

[0004] K. A. Mauritz et al., Polym. Mater. Sci. Eng. 58,1079-1082(1988), in an article titled “Nafion-based Microcomposites:Silicon Oxide-filled Membranes”, discuss the formation of microcomposite membranes by the growth of silicon oxide microclusters orcontinuous silicon oxide interpenetrating networks in pre-swollen“NAFION®” sulfonic acid films. “NAFIONO®” is a registered trademark ofE. I. du Pont de Nemours and Company.

[0005] U.S. Pat. No. 5,094,995 discloses catalysts comprisingperfluorinated ion-exchange polymers (PFIEP) containing pendant sulfonicacid groups supported on an inert carrier having a hydrophobic surfacecomprising calcined shot coke.

[0006] U.S. Pat. No. 4,038,213 discloses the preparation of catalystscomprising perfluorinated ion-exchange polymers (PFIEP) containingpendant sulfonic acid groups on a variety of supports.

[0007] The catalytic utility of perfluorinated ion-exchange polymers(PFIEP) containing pendant sulfonic acid groups, supported andunsupported has been broadly reviewed: G. A. Olah et al., Synthesis,513-531(1986) and F. J. Waller, Catal. Rev.-Sci. Eng., 1-12(1986).

SUMMARY OF THE INVENTION

[0008] This invention provides a porous microcomposite comprisingperfluorinated ion-exchange polymer containing pendant sulfonic and/orcarboxylic acid groups entrapped within and highly dispersed throughouta network of metal oxide, wherein the weight percentage ofperfluorinated ion-exchange polymer in the microcomposite is from about0.1 to 90 percent, preferably from about 5 to about 80 percent, andwherein the size of the pores in the microcomposite is about 0.5 nm toabout 75 nm.

[0009] In a separate embodiment, the microcomposite can simultaneouslycontain larger pores ranging from about 75 nm to about 1000 nm, whereinthese larger pores are formed by introducing acid-extractable fillerparticles during the formation process.

[0010] This invention further provides the process of preparation of aporous microcomposite which comprises perfluorinated ion-exchangepolymer containing pendant sulfonic and/or carboxylic acid groupsentrapped within and highly dispersed throughout a network of metaloxide, wherein the weight percentage of perfluorinated ion-exchangepolymer in the microcomposite is from about 0.1 to 90 percent, andwherein the size of the pores in the microcomposite is about 0.5 nm toabout 75 nm;

[0011] said process comprising the steps of:

[0012] a. mixing the perfluorinated ion-exchange polymer with one ormore metal oxide precursors in a common solvent;

[0013] b. initiating gelation;

[0014] c. allowing sufficient time for gelation and aging of themixture; and

[0015] d. removing the solvent.

[0016] In a further preferred embodiment the process further comprisesat step (a), adding to the mixture an amount from about 1 tot 80 weightpercent of an acid extractable filler particle, after d;

[0017] e. acidifying the product of step d by the addition of acid; and

[0018] f. removing the excess acid from the microcomposite;

[0019] to yield a microcomposite further containing pores in the rangeof about 75 nm to about 1000 nm.

[0020] The present invention also provides an improved process for thenitration of an aromatic compound wherein the improvement comprisescontacting said aromatic compound with a catalytic microcomposite of thepresent invention, described above.

[0021] The present invention further provides an improved process forthe esterification of a carboxylic acid with an olefin wherein theimprovement comprises contacting said carboxylic acid with a catalyticmicrocomposite of the present invention, described above.

[0022] The present invention also provides an improved process for thepolymerization of tetrahydrofuran wherein the improvement comprisescontacting said tetrahydrofuran with a catalytic microcomposite of thepresent invention, described above.

[0023] The present invention further provides an improved process forthe alkylation of an aromatic compound with an olefin wherein theimprovement comprises contacting said aromatic compound with a catalyticmicrocomposite of the present invention, described above.

[0024] The present invention provides an improved process for theacylation of an aromatic compound with an acyl halide wherein theimprovement comprises contacting said aromatic compound with a catalyticmicrocomposite of the present invention, described above.

[0025] The present invention further provides an improved process forthe dimerization of an alpha substituted styrene, wherein theimprovement comprises contacting said alpha substituted styrene with acatalytic microcomposite of the present invention, described above.

[0026] The present invention further provides a process for regeneratinga catalyst comprising a microcomposite of the present invention, asdescribed above, comprising the steps of: mixing the microcomposite withan acid, and removing the excess acid.

[0027] The present invention also provides a process for theisomerization of an olefin comprising contacting said olefin atisomerization conditions with a catalytic amount of a porousmicrocomposite, said microcomposite comprising perfluorinatedion-exchange polymer containing pendant sulfonic and/or carboxylic acidgroups entrapped within and highly dispersed throughout a network ofmetal oxide, wherein the weight percentage of perfluorinatedion-exchange polymer in the microcomposite is from about 0.1 to 90percent, preferably from about 5 to about 80 percent, most preferablyfrom about 5 to about 20 percent and wherein the size of the pores inthe microcomposite is about 0.5 nm to about 75 nm.

BRIEF DESCRIPTION OF THE DRAWINGS

[0028]FIG. 1 is a graph showing data from Example 58 and Table 4b whichshows the effect of contact time at 50° C. and He/1-butene=1.2/1.0 on1-butene isomerization over a 13 wt % “NAFION®” PFIEP/silicamicrocomposite prepared as in Example 16.

DETAILED DESCRIPTION OF THE INVENTION

[0029] The organic-inorganic polymer microcomposites of the presentinvention are high surface area, porous microcompositions which exhibitexcellent catalytic activity. Whereas the surface area of “NAFIONO®” NR50 PFIEP, a commercial product, is approximately 0.02 m² per gram, apreferred embodiment of the present invention comprises microcompositesof PFIEP and silica having a surface area typically of 5 to 500 m² pergram. The composition of the present invention exists as a particulatesolid which is porous and glass-like in nature, typically 0.1-4 mm insize and structurally hard, similar to dried silica gels. Theperfluorinated ion exchange polymer (PFIEP) is highly dispersed withinand throughout the silica network of the microcomposite of the presentinvention, and the microstructure is very porous. The porous nature ofthis material is evident from the high surface areas measured for theseglass-like pieces, having typical pore diameters in the range of 1-25nm. Another preferred embodiment is the use of the present invention inpulverized form.

[0030] In another preferred embodiment, macroporosity (pore sizes about75 to about 1000 nm) is also introduced into the microcomposite,resulting in a microcomposite having both increased surface area fromthe micropores and mesopores (0.5-75 nm) and enhanced accessibilityresulting from the macropores (75-1000 nm).

[0031] Perfluorinated ion-exchange polymers (PFIEP) containing pendantsulfonic acid, carboxylic acid, or sulfonic acid and carboxylic acidgroups used in the present invention are well known compounds. See, forexample, Waller et al., Chemtech, July, 1987, pp. 438-441, andreferences therein, and U.S. Pat. No. 5,094,995, incorporated herein byreference. Perfluorinated ion-exchange polymers (PFIEP) containingpendant carboxylic acid groups have been described in U.S. Pat. No.3,506,635, which is also incorporated by reference herein. Polymersdiscussed by J. D. Weaver et al., in Catalysis Today, 14 (1992) 195-210,are also useful in the present invention. Polymers that are suitable foruse in the present invention have structures that include asubstantially fluorinated carbon chain that may have attached to it sidechains that are substantially fluorinated. In addition, these polymerscontain sulfonic acid groups or derivatives of sulfonic acid groups,carboxylic acid groups or derivatives of carboxylic acid groups and/ormixtures of these groups. For example, copolymers of a first fluorinatedvinyl monomer and a second fluorinated vinyl monomer having a pendantcation exchange group or a pendant cation exchange group precursor canbe used, e.g., sulfonyl fluoride groups (SO₂F) which can be subsequentlyhydrolyzed to sulfonic acid groups. Possible first monomers includetetrafluoroethylene (TFE), hexafluoropropylene, vinyl fluoride,vinylidine fluoride, trifluoroethylene, chlorotrifluoroethylene,perfluoro (alkyl vinyl ether), and mixtures thereof. Possible secondmonomers include a variety of fluorinated vinyl ethers with pendantcation exchange groups or precursor groups. Preferably, the polymercontains a sufficient number of acid groups to give an equivalent weightof from about 500 to 20,000, and most preferably from 800 to 2000.Representative of the perfluorinated polymers for use in the presentinvention are “NAFION®” PFIEP (a family of polymers for use in themanufacture of industrial chemicals, commercially available from E. I.du Pont de Nemours and Company), and polymers, or derivatives ofpolymers, disclosed in U.S. Pat. Nos. 3,282,875; 4,329,435; 4,330,654;4,358,545; 4,417,969; 4,610,762; 4,433,082; and 5,094,995. Morepreferably the polymer comprises a perfluorocarbon backbone and apendant group represented by the formula —OCF₂CF(CF₃)OCF₂CF₂SO₃X,wherein X is H, an alkali metal or NH₄. Polymers of this type aredisclosed in U.S. Pat. No. 3,282,875.

[0032] Typically, suitable perfluorinated polymers are derived fromsulfonyl group-containing polymers having a fluorinated hydrocarbonbackbone chain to which are attached the functional groups or pendantside chains which in turn carry the functional groups.Fluorocarbosulfonic acid catalysts polymers useful in preparing themicrocomposites of the present invention have been made by Dow Chemicaland are described in Catalyis Today, 14 (1992) 195-210. Otherperfluorinated polymer sulfonic acid catalysts are described inSynthesis, G. I. Olah, P. S. Iyer, G. K. Surya Prakash, 513-531 (1986).

[0033] There are also several additional classes of polymer catalystsassociated with metal cation ion-exchange polymers and useful inpreparing the microcomposite of the present invention. These comprise 1)a partially cation-exchanged polymer, 2) a completely cation-exchangedpolymer, and 3) a cation-exchanged polymer where the metal cation iscoordinated to another ligand (see U.S. Pat. No. 4,414,409, and Waller,F. J. In Polymeric Reagents and Catalysts; Ford, W. T., Ed.,; ACSSymposium Series 308; American Chemical Society; Washington, D.C., 1986,Chapter 3).

[0034] Preferred PFIEP suitable for use in the present inventioncomprise those containing sulfonic acid groups. Most preferred is asulfonated “NAFION®” PFIEP.

[0035] Perfluorinated ion-exchange polymers are used within the contextof the invention in solution form. It is possible to dissolve thepolymer by heating it with an aqueous alcohol to about 240° C. or higherfor several hours in a high pressure autoclave (see U.S. Pat. No.4,433,082 or Martin et al., Anal. Chem., Vol. 54, pp 1639-1641 (1982).Other solvents and mixtures may also be effective in dissolving thepolymer.

[0036] Ordinarily, for each part by weight of polymer employed to bedissolved, from as little as about 4 or 5 parts by weight up to about100 parts by weight, preferably 20-50 parts by weight, of the solventmixture are employed. In the preparation of the dissolved polymer, thereis an interaction between the equivalent weight of the polymer employed,the temperature of the process, and the amount and nature of the solventmixture employed. For higher equivalent weight polymers, the temperatureemployed is ordinarily higher and the amount of liquid mixture employedis usually greater.

[0037] The resulting mixture can be used directly and may be filteredthrough fine filters (e.g., 4-5.5 micrometers) to obtain clear, thoughperhaps slightly colored, solutions. The mixtures obtained by thisprocess can be further modified by removing a portion of the water,alcohols and volatile organic by-products by distillation.

[0038] Commercially available solutions of perfluorinated ion-exchangepolymers can also be used in the preparation of the microcomposite ofthe present invention (e.g., at 5 wt % solution of a perfluorinatedion-exchange powder in a mixture of lower aliphatic alcohols and water,Cat. No. 27,470-4, Aldrich Chemical Company, Inc., 940 West Saint PaulAvenue, Milwaukee, Wis. 53233).

[0039] “Metal oxide” signifies metallic or semimetallic oxide compounds,including, for example, alumina, silica, titania, germania, zirconia,alumino-silicates, zirconyl-silicates, chromic oxides, germanium oxides,copper oxides, molybdenum oxides, tantalum oxides, zinc oxides, yttriumoxides, vanadium oxides, and iron oxides. Silica is most preferred. Theterm “metal oxide precursor” refers to the form of the metal oxide whichis originally added in the sol-gel process to finally yield a metaloxide in the final microcomposite. In the case of silica, for example,it is well known that a range of silicon alkoxides can be hydrolyzed andcondensed to form a silica network. Such precursors astetramethoxysilane (tetramethyl orthosilicate), tetraethoxysilane(tetraethyl orthosilicate), tetrapropoxysilane, tetrabutoxysilane, andany compounds under the class of metal alkoxides which in the case ofsilicon is represented by Si(OR)₄, where R includes methyl, ethyl,n-propyl, iso-propyl, n-butyl, sec-butyl, iso-butyl, tert-butyl or whereR is a range of organic groups, such as alkyl. Also included as aprecursor form is silicon tetrachloride. Further precursor formscomprise organically modified silica, for example, CH₃Si(OCH₃)₃,PhSi(OCH₃)₃, and (CH₃)₂Si(OCH₃)₂. Other network formers include metalsilicates, for example, potassium silicate, sodium silicate, lithiumsilicate. K, Na or Li ions can be removed using a DOWEX® cation exchangeresin (sold by Dow Chemical, Midland, Mich., which generates polysilicicacid which gels at slightly acid to basic pH. The use of “LUDOX®”colloidal silica (E. I. du Pont de Nemours and Company, Wilmington,Del.) and fumed silica (“CAB-O-SIL®” sold by Cabot Corporation ofBoston, Mass.) which can be gelled by altering pH and adjusting theconcentration in solution will also yield a metal oxide network in themicrocomposite of the invention. For example, typical precursor forms ofsilica are Si(OCH₃)₄, Si(OC₂H₅)₄ and Na₂SiO₃; and a typical precursorform of alumina is aluminum tri-secbutoxide Al(OC₄H₉)₃.

[0040] “Acid extractable filler particles” which are used in the processof the invention to introduce macropores of about 75 to about 1000 nminto the microcomposite include particles which are insoluble in thepreparative gel-forming solvent, but are acid soluble and extractablefrom the formed microcomposite. Such filler particles include, forexample, alkali metal carbonates or alkaline earth carbonates, such ascalcium carbonate, sodium carbonate and potassium carbonate.

[0041] The first stage of the process for the preparation of themicrocomposite of the present invention involves preparing a gelsolution that contains both the perfluorinated ion-exchange polymer(PFIEP) containing pendant sulfonic acid groups and/or pendantcarboxylic acid groups and one or more metal oxide precursors in acommon solvent.

[0042] This solvent normally comprises water and various lower aliphaticalcohols such as methanol, 1-propanol, 2-propanol, mixed ethers andn-butanol. Thus, in some cases the water necessary for gel formation canbe supplied by the water in the reaction solvent. Other polar solventswhich may be suitable for the particular metal oxide precursor/polymerselected include acetonitrile, dimethyl formamide, dimethylsulfoxide,nitromethane, tetrahydrofuran and acetone. Toluene, alkanes andfluorocarbon-containing solvents can also be useful in some instances tosolubilize the polymer.

[0043] Gelation may in some instances self-initiate, for example, whenwater is present in the common solvent, or via rapid drying, such asspray drying. In other instances, gelation must be initiated, which canbe achieved in a number of ways depending on the initial mixture ofpolymer, metal oxide precursor and solvent selected. Gelation isdependent on a number of factors such as the amount of water present,because water is required for the hydrolysis and condensation reaction.Other factors include temperature, solvent type, concentrations, pH,pressure and the nature of the acid or base used. The pH can be achievedin a number of ways, for example, by adding base to the PFIEP solutionor by adding the PFIEP solution to the base, or by adding the metaloxide to the solution than adjusting pH with acid or base. Anothervariable in addition to the mode of addition for achievement of pH isthe concentration of base employed. Gels can also be formed by acidcatalyzed gellation. See Sol-Gel Science, Brinker, C. J. and Scherer, G.W., Academic Press, 1990. Non-gelled PFIEP/metal oxide solution may bespray dried to yield dried PFIEP/metal oxide composites.

[0044] Time required for the gel forming reaction can vary widelydepending on factors such as acidity, temperature, and concentration. Itcan vary from practically instantaneous to several days.

[0045] The gel forming reaction can be carried out at virtually anytemperature at which the solvent is in liquid form. The reaction istypically carried out at room temperature.

[0046] Pressure over the gel forming reaction is not critical and mayvary widely. Typically the reaction is carried out at atmosphericpressure. The gel forming reaction can be carried out over a wide rangeof acidity and basicity depending upon the amount of base added to thegel precursor.

[0047] After formation, but before isolation, the gel, still in thepresence of its reaction solvent, may be allowed to stand for a periodof time. This is referred to as aging.

[0048] The product is dried at room temperature or at elevatedtemperatures in an oven for a time sufficient to remove solvent. Dryingcan be done under vacuum, or in air or using an inert gas such asnitrogen. Optionally, after aging and/or removal of the solvent, thehard glass-like product can be ground and passed through a screen,preferably a 10-mesh screen. Grinding generates smaller particles (andgreater surface area) which are more readily re-acidified. Grinding isespecially useful for microcomposites having a high weight percent ofPFIEP.

[0049] Preferably, following removal of the solvent and optionalgrinding, the material is reacidified, washed and filtered. This may berepeated a number of times. Reacidification of the material converts,for example, the sodium salt of the perfluorosulfonic acid into theacidic, active form. Suitable acids comprise HCl, H₂SO₄ and nitric acid.

[0050] A number of reaction variables, for example acidity, basicity,temperature, aging, method of drying and drying time of gels, have beenfound to affect the pore size and pore size distribution. Both higher pHand longer aging of gels (before solvent removal) lead to larger finalpore size in the dried PFIEP/metal oxide gels. Pore size can be variedover a wide range (about 0.5 to about 75 nm) depending on the variablesdescribed above. Aging of the wet gels (in the presence of the solvent)for a few hours at 75° C. also leads to an increase in pore sizealthough over a smaller range. This effect is characteristic of silicatype gels, where the aging effect gives rise to an increasingly crosslinked network which upon drying is more resistant to shrinkage and thusa higher pore size results. See, for example, the text Sol-Gel Science,Brinker, C. J. and Scherer, G. W., Academic Press, 1990, pp. 51.8-523.In the present invention, preferred pore size is about about 0.1 nm toabout 75 nm, more preferred about 0.5 to about 50 nm, most preferred isabout 0.5 to about 30 mm.

[0051] Microcomposites comprising macropores (about 75 to about 1000 nm)have also been developed hereunder which have both high surface area andmicro-, meso- and macroporosity. Such a structure is easily accessiblefor catalytic and ion exchange purposes. This unique microstructure ofthe present invention is prepared by adding sub-micron size particles ofcalcium carbonate to a PFIEP/metal oxide precursor solution prior to thegelation step. Upon acidification of the glass gels, the calciumcarbonate dissolves out leaving large (about 50(nm) pores connectedthroughout the matrix with a sub-structure of about 10 nm micropores.This kind of structure offers a high surface area PFIEP/metal oxidenetwork within the microcomposite which is readily accessiblethroughout. Macroporosity can be achieved by adding approximately 1 to80 wt % (based upon gel weight) of acid-extractable filler particlessuch as calcium carbonate, to the sol-gel process prior to the gelationstep.

[0052] It is believed that the highly porous structure of themicrocomposites of the present invention consists of a continuous metaloxide phase which entraps a highly dispersed PFIEP within and throughouta connected network of porous channels. The porous nature of thematerial can be readily demonstrated, for example, by solventabsorption. The microcomposite can be observed to emit bubbles which areevolved due to the displacement of the air from within the porousnetwork.

[0053] The distribution of the PFIEP entrapped within and throughout themetal oxide is on a very fine sub-micron scale. The distribution can beinvestigated using electron microscopy, with energy dispersive X-rayanalysis, which provides for the analysis of the elements Si and O (whenusing silica, for example) and C and F from the PFIEP fluoropolymer.Fractured surfaces within a particle and several different particles forcompositions ranging from 10 to 40 wt % “NAFION®” PFIEP were analyzed,and all of the regions investigated showed the presence of both thesilica and PFIEP polymer from the edge to the center of themicrocomposite particles; thus the microcomposite exhibited an intimatemixture of Si and F. No areas enriched in entirely Si or entirely F wereobserved, rather a uniform distribution of Si and F was seen. Thisbicomponent description is believed to be accurate for areas as low 0.1micrometer in size. The morphology of the microcomposites, as preparedby Example 1, is somewhat particulate in nature, again as observed usingscanning electron microscopy. This is typical of silica gel typematerial prepared using this sol-gel procedure. The primary particlesize is on the order of 5-10 nm. This was also confirmed using smallangle x-ray scattering experiments on the material, which revealed adomain size in the range of 5-10 nm. The data is consistent with thePFIEP being entrapped within and highly dispersed throughout the silica.

[0054] The microcomposites of the invention are useful as ion exchangeresins, and as catalysts, for example, for alkylating aliphatic oraromatic hydrocarbons, for decomposing organic hydroperoxides, such ascumene hydroperoxide, for sulfonating or nitrating organic compounds,and for oxyalkylating hydroxylic compounds. A serious drawback to thecommercial use of previous perfluorocarbon sulfonic acid catalysts hasbeen their high cost and relatively low catalytic activity. The presentinvention provides the benefits of reduced costs, higher catalyticactivity, and in some cases improved reaction selectivity. Othercommercially important applications for PFIEP/silica catalysts of thepresent invention comprise hydrocarbon isomerizations andpolymerizations; carbonylation and carboxylation reactions; hydrolysisand condensation reactions, esterifications and etherification;hydrations and oxidations; aromatic acylation, alkylation and nitration;and isomerization and metathesis reactions.

[0055] The present invention provides an improved process for thenitration of an aromatic compound wherein the improvement comprisescontacting the aromatic compound with a microcomposite of the presentinvention as a catalyst. For example, in the nitration of benzene, asolution comprising benzene and optionally, a desiccant such as MgSO₄,is heated, typically to reflux at atmospheric pressure under an inertatmosphere, and a nitrating agent, for example, HNO₃ is added. Theprocess is conducted under normal nitration conditions which conditions,such as temperature, are dependent upon the reactivity of the aromaticused. When a microcomposite of the present invention is used as acatalyst in the benzene solution, a high rate of conversion andselectivity to nitrobenzene is demonstrated as compared to “NAFION®”PFIEP alone or to the use of no catalyst (see Table I, Example 42). Apreferred catalyst for this process is a microcomposite of the presentinvention wherein the perfluorinated ion-exchange polymer containspendant sulfonic acid groups and wherein the metal oxide is silica,alumina, titania, germania, zirconia, alumino-silicate,zirconyl-silicate, chromic oxide and/or iron oxide. Most preferred iswherein the perfluorinated ion-exchange polymer is a “NAFION®” PFIEP andthe metal oxide is silica, the most preferred “NAFION®” PFIEP havingapproximately 6.3 tetrafluoroethylene (TFE) molecules for everyperfluoro perfluoro(3,6-dioxa-4-methyl-7-octenesulfonyl fluoride)molecule (CF₂ ═CF—O—[CF₂CF(CF₃)]—O—CF₂CF₂—SO₂F (PSEPVE)) and anequivalent weight of approximately 1070.

[0056] The present invention further provides an improved process forthe esterification of a carboxylic acid by reaction with an olefinwherein the improvement comprises contacting said carboxylic acid with aporous microcomposite of the present invention as a catalyst. Forexample, the esterification of acetic acid with cyclohexene to yieldcyclohexylacetate. This esterification is typically carried out in areactor. The acetic acid and cyclohexene solution typically comprisesexcess acetic acid to minimize dimerization of the cyclohexene.Generally, the reaction is run under normal esterification conditionswhich conditions are dependent upon the reactivity of the carboxylicacid and olefin used. Using as catalyst a microcomposite of the presentinvention results in specific activity almost an order of magnitudehigher than that of other catalysts (see Table II, Example 43). Apreferred catalyst for this process is a microcomposite of the presentinvention wherein the perfluorinated ion-exchange polymer containspendant sulfonic acid groups and wherein the metal oxide is silica,alumina, titania, germania, zirconia, alumino-silicate,zirconyl-silicate, chromic oxide and/or iron oxide. Most preferred iswherein the perfluorinated ion-exchange polymer is a “NAFION®” PFIEP andthe metal oxide is silica, the most prefered “NAFION®” PFIEP havingapproximately 6.3 tetrafluoroethylene (TFE) molecules for everyperfluoro perfluoro(3,6-dioxa-4-methyl-7-octenesulfonyl fluoride)molecule (CF₂═CF—O—[CF₂CF(CF)]—O—CF₂CF₂—SO₂F (PSEPVE)) and has anequivalent weight of approximately 1070.

[0057] The present invention also provides an improved process for thealkylation of an aromatic compound with an olefin wherein theimprovement comprises using the microcomposite of the present inventionas a catalyst. For example, in the alkylation of toluene with n-heptene,the toluene and heptene are dried before use and then mixed and heated,for example, to about 100° C. Dried catalyst comprising the porousmicrocomposite of the present invention is added to thetoluene/n-heptene solution and left to react. This improved process isgenerally conducted under normal alkylation conditions which conditionsare dependent upon the reactivity of the aromatic and olefin used. Ahigh rate of conversion is found using a microcomposite of the presentinvention as compared to using “NAFION®” NR 50 PFIEP as the catalyst.The preferred catalyst for this process is a microcomposite of thepresent invention wherein the perfluorinated ion-exchange polymercontains pendant sulfonic acid groups and wherein the metal oxide issilica, alumina, titania, germania, zirconia, alumino-silicate,zirconyl-silicate, chromic oxide and/or iron oxide. Most preferred iswherein the perfluorinated ion-exchange polymer is a “NAFION®” PFIEP andthe metal oxide is silica, the most preferred “NAFION®” PFIEP havingapproximately 6.3 tetrafluoroethylene (TFE) molecules for everyperfluoro perfluoro(3,6-dioxa-4-methyl-7-octenesulfonyl fluoride)molecule (CF₂═CF—O—[CF₂CF(CF₃)]—O—CF₂CF₂—SO₂F (PSEPVE)) and has anequivalent weight of approximately 1070.

[0058] The present invention also provides an improved process for thepolymerization of tetrahydrofuran to polytetrahydrofuran. The product ispolytetramethylene ether acetate (PTMEA), the diacetate ofpolytetrahydrofuran, which can be used in the preparation of“TERATHANE®” polyether glycol (E. I. du Pont de Nemours and Company,Wilmington, Del.). A process for the polymerization of tetrahydrofurangenerally comprises contacting tetrahydrofuran with acetic anhydride andacetic acid in solution usually within a pressure reactor equipped withan agitator. The reaction can be conducted at ambient temperature. Theimprovement herein comprises adding to the solution as a catalyst theporous microcomposite of the present invention. Contact time can rangefrom 1 hr to 24 hrs.

[0059] The present invention further provides an improved process forthe acylation of an aromatic compound with an acyl halide to form anaryl ketone. A process for the acylation of an aromatic compoundgenerally comprises heating the compound with the acyl halide. Theimprovement herein comprises contacting the aromatic compound with acatalytic porous microcomposite of the present invention. After allowingsufficient time for tie reaction to complete, the aryl ketone product isrecovered.

[0060] The present invention also provides an improved process for thedimerization of an alpha substituted styrene. The improvement comprisescontacting the styrene with a catalytic porous microcomposite of thepresent invention. When using alpha methyl styrene, for example, thestyrene may be heated in solution and the catalyst added. The productcomprises a mixture of unsaturated dimers(2,4-diphenyl-4-methyl-1-pentene and 2,4-diphenyl-4-methyl-2-pentene)and saturated dimers (1,1,3-trimethyl-3-phenylidan and cis andtrans-1,3-dimethyl-1,3-diphenylcyclobutane).

[0061] A preferred catalyst for the polymerization of tetrahydrofuran,for the acylation of an aromatic compound and for the dimerization of analpha substituted styrene is a microcomposite of the present inventionwherein the perfluorinated ion-exchange polymer contains sulfonic acidgroups and wherein the metal oxide is silica, alumina, titania,germania, zirconia, alumino-silicate, zirconyl silicate, chromic oxideand/or iron oxide. Most preferred is wherein the PFIEP is a “NAFION®”PFIEP and the metal oxide is silica, the most preferred “NAFION®” PFIEPhaving approximately 6.3 tetrafluoroethylene (TFE) molecules for everyperfluoro perfluoro(3,6-dioxa-4-methyl-7-octenesulfonyl fluoride)molecule (CF₂═CF—O—[CF₂CF(CF)]—O—CF₂CF₂—SO₂F (PSEPVE)) and has anequivalent weight of approximately 1070.

[0062] The microcomposite product of the present invention can beconverted to a metal cation-exchanged material, as described by Waller(Catal. Rev. Sci. Eng. 28(1), 1-12 (1986)) for PFIEP resins. Suchmaterials are also useful as catalysts.

[0063] Traditionally, olefin isomerization and alkylation with paraffinshave been catalyzed by liquid mineral acids such as H₂SO₄, HF or AlCl₃.Environmental concerns associated with corrosive mineral acid catalystshave encouraged process changes and the development of solid-bedcatalyst processes.

[0064] It is especially desirable to convert 1-butene to 2-butenes priorto use in the HF catalyzed alkylation process because the quality of thealkylates from 2-butenes (96-98 research octane number (RON) aresignificantly better than that from the 1-butene feed (87-89 RON).Extensive studies have been carried out on the solid acid catalyzed1-butene isomerization to 2-butenes and to isobutene. 1-Buteneisomerization to 2-butenes has been widely used as a model reaction ofcharacterizing solid acid catalysts as well. It is clear that 1-buteneisomerization to 2-butenes is not a very demanding reaction in terms ofacid strength; several of solid acid are capable of catalyzing thisisomerization involving the double bond shifting reaction. However,there remain important incentives for developing catalysts that canoperate efficiently at lower temperatures. First, competingoligomerization reactions which not only result in yield losses, butalso lead to catalyst deactivation generally become more significant athigher temperatures. Second, the equilibrium isomer distributionincreasingly favors 2-butenes at lower temperatures.

[0065] Various solid acid catalysts and even amorphous silica-aluminaare capable of catalyzing the 1-butene isomerization to 2-butenes atnear ambient temperatures, but rapid deactivation is frequentlyencountered. Acidic cation exchange resin, sulfonicstyrene-divinylbenzene copolymer (“AMBERLYST 15®”) was shown to beactive for the 1-butene isomerization to 2-butenes (see T. Uematsu,Bull. Chem. Soc. Japan, 1972, 45, 3329).

[0066] The present invention provides a process for the isomerization ofan olefin comprising contacting said olefin at isomerization conditionswith a catalytic amount of the microcomposite of the present invention.

[0067] Olefin isomerization processes can be directed towards eitherskeletal isomerization, double bond isomerization or geometricisomerization. Skeletal isomerization is concerned with reorientation ofthe backbone of the carbon structure, for example 1-butene to isobutene.Double bond isomerization is concerned with relocation of the doublebond between carbon atoms while maintaining the backbone of the carbonstrucuture, for example 1-butene to 2-butene. Conversions between, forexample cis and trans 2-pentenes, are known as geometric isomerization.The present invention provides primarily for double bond isomerizationand includes some geometric isomerization. Skeletal isomerization isalso provided to a limited degree at higher temperatures.

[0068] Preferred olefins are C₄ to C₄₀ hydrocarbons having at least onedouble bond, the double bond(s) being located at a terminal end, aninternal position or at both a terminal and internal position. Mostpreferred olefins have 4 to 20 carbon atoms. The olefin can bestraight-chained (normal) or branched and may be a primary or secondaryolefin and thus substituted with one or more groups that do notinterfere with the isomerization reaction. Such substituted groups thatdo not interfere with the isomerization reaction could include alkyl,aryl, halide, alkoxy, esters, ethers, or thioethers. Groups that mayinterfere with the process would be alcohols, carboxylic acids, amines,aldhehydes and ketones. The porous microcomposite used in the presentprocess is described in detail above and comprises a perfluorinatedion-exchange polymer containing pendant sulfonic and/or carboxylic acidgroups entrapped within and highly dispersed throughout a network ofmetal oxide, wherein the weight percentage of perfluorinatedion-exchange polymer in the microcomposite is from about 0.1 to 90percent, preferably from about 5 to about 80 percent, most preferablyfrom about 5 to about 20 percent and wherein the size of the pores inthe microcomposite is about 0.5 nm to about 75 nm.

[0069] A preferred catalyst for the present olefin isomerization processis the microcomposite of the present invention wherein theperfluorinated ion-exchange polymer contains pendant sulfonic acidgroups and wherein the metal oxide is silica, alumina, titania,germania, zirconia, alumino-silicate, zirconyl-silicate, chromic oxideand/or iron oxide. Most preferred is wherein the perfluorinatedion-exchange polymer is a “NAFION®” PFIEP and the metal oxide is silica,the most preferred “NAFION®” PFIEP” having approximately 6.3 moles oftetrafluoroethylene (TFE) per mole of perfluoroperfluoro(3,6-dioxa-4-methyl-7-octenesulfonyl fluoride) molecule(CF₂═CF—O—[CF₂CF(CF₃)]—O—CF₂CF₂—SO₂F (PSEPVE)) and an equivalent weightof approximately 1070.

[0070] In another embodiment, macroporosity (pore sizes about 75 toabout 1000 nm) is also introduced into the microcomposite used in thepresent olefin isomerization process, resulting in the microcompositehaving both increased surface area from the micropores and mesopores(0.5-75 nm) and enhanced accessibility resulting from the macropores(75-1000 nm).

[0071] Contacting of the olefin with the catalyst can be effected byusing the catalyst in a fixed-bed system, a moving-bed system, afluidized-bed system, or in a batch-type operation. Reactants cancontact the catalyst in the liquid phase, a mixed vapor-liquid phase, ora vapor phase. The reactants can contact the catalyst in the absence ofhydrogen or in the presence of hydrogen in a molar ratio of hydrogen toolefin of from about 0.01 to about 10. “Absence of hydrogen” means thatfree or molecular hydrogen is substantially absent in the combinedreactant feed to the process. Hydrogen, if present, can be suppliedtotally from outside the isomerization process, or the outside hydrogenmay be supplemented by hydrogen separated from reaction products andrecycled. Inert diluents such as helium, nitrogen, argon, methane,ethane and the like can be present either in association with hydrogenor in the absence of hydrogen. Although the principal isomerizationreaction does not consume hydrogen, there can be net consumption ofhydrogen in side reactions.

[0072] The isomerization of olefins is well known to be limited by thethermodynamic equilibrium of the reacting species. Isomerizationconditions for the present process comprise reaction temperaturesgenerally in the range of about 0° C. to about 300° C., preferably fromabout 25° C. to about 250° C. Pressure can range from ambient for gasphase or pressure sufficient to keep reaction in the liquid phase.Reactor operating pressures usually will range from about one atmosphereto about 100 atmospheres, preferably from about one atmosphere to about50 atmospheres. The amount of catalyst in the reactor will provide anoverall weight hourly space velocity (WHSV) of from about 0.1 to 100hr⁻¹, preferably from about 0.1 to 10 hr⁻¹; most preferably 0.1 to 2hr⁻¹.

[0073] Long contact time during olefin isomerization can createundesirable by-products, such as oligomers. The process of the presentinvention utilizes short contact times which cuts down on the amount ofundesirable by-products. Contact times for the present process rangefrom about 0.01 hr to about 10 hrs; preferably 0.1 hr to about 5 hrs.Contact time may be reduced at higher temperatures.

[0074] The particular product-recovery scheme employed is not deemed tobe critical to the present invention; any recovery scheme known in theart may be used. Typically, the reactor effluent will be condensed andthe hydrogen and inerts removed therefrom by flash separation. Thecondensed liquid product then is fractionated to remove light materialsfrom the liquid product. The selected isomers may be separated from theliquid product by adsorption, fractionation, or extraction.

[0075] Olefin isomerization is useful in converting compounds intoisomers more useful for particular applications. Olefins with the doublebond at a terminal end tend to be more reactive and are easy to oxidizewhich can cause problems with their storage. Therefore, a shift to amore stable form can be desirable.

[0076] A high rate of conversion is found using the microcomposite ofthe present invention. Data in FIG. 1 shows that the microcomposite isvery efficient for the 1-butene to 2-butenes isomerization reactionunder mild conditions. Even at 50° C., near thermodynamic equilibriumvalues are obtained, which at 50° C. are 4.1%, 70.5% and 25.4% for1-butene, trans-2-butene and cis-2-butene, respectively, and theexperimental data are 6.6%, 66.9% and 26.5%, respectively at WHSV of1-butene of 1 hr⁻¹. The effective activation energy for 1-buteneisomerization to 2-butenes was determined to be 16.0 kcal/mol over the13 wt % “NAFION®” PFIEP/silica microcomposite used (see Example 58).Comparisons performed in Example 57 show that “NAFION®” NR50 at 50° C.produced less than 1% conversion of the 1-butene, and at a temperaturewhich could effectively catalyze the butene (200° C.) significantoligomers are also formed.

[0077] A study on the effect of temperature was carried out with a verydiluted feed of 1-butene and at very low WHSV of 1-butene (see Table 4a,Example 58). Since near equilibrium n-butene distribution was obtainedat 50° C., the main interest was on the isobutene formation. However,extremely small amounts, well below the equilibrium concentration, ofisobutene was formed even at the highest temperature employed (250° C.).Due to the very low WHSV of 1-butene employed (Table 4a), the oligomersformed were quite pronounced. However, oligomers as well as isobuteneformed over the microcomposite catalyst were less than that producedfrom the “NAFION®” NR50 beads catalyst under the same reactionconditions (see Table 2a, Example 57), and they are both in negligibleamounts at low temperatures (<100° C.). Even though no pronouncedcatalyst deactivation was observed over more than 12 hr for the 1-buteneisomerization to 2-butenes, the formation of isobutene and oligomersdecreased rather rapidly at temperatures >100° C. The data listed in theTables are obtained after about one hour on stream in all cases. Theseresults suggest that isobutene could be formed through, the cracking ofbutene oligomers which are favored at this temperature and low WHSV or1-butene.

[0078] Overall, the extremely low surface area “NAFION®” NR50 beadsresult in low activity for the 1-butene isomerization under the reactionconditions employed. However, the intrinsic isomerization activity ofthe active sites in “NAFION®” is high and when present in a moreaccessible microstructure it becomes a very effective catalyst. Veryhigh catalytic activity was observed for the 13 wt % “NAFION®”PFIEP/silica microcomposite material for which equilibrium distributionof n-butene can be readily obtained at 50° C. and is about 5-6 timesmore active than the “AMBERLYST 15®” catalyst.

[0079] The microcomposite product of the present invention is useful ina range of catalytic reactions as described above. For some of thesereactions, some brown coloration may form upon the catalyst. Catalystsof the present invention can be regenerated by treatment with an acid,for example nitric acid. The microcomposite catalyst is contacted withthe acid and then stirred at a temperature ranging from about 15° C. toabout 100° C. for about 1 hr to about 26 hrs. Subsequent washing withde-ionized water is used to remove excess acid. The catalyst is thendried at a temperature ranging from about 100° C. to about 200° C.,preferably under vacuum for about 1 hr to about 60 hrs to yield theregenerated catalyst.

EXAMPLES

[0080] “NAFION®” PFIEP solutions can be purchased from Aldrich ChemicalCo., Milwaukee, Wis., or PFIEP solutions generally can be prepared usingthe procedure of U.S. Pat. Nos. 5,094,995 and 4,433,082. The “NAFION®”PFIEP solution referred to in the examples below is, unless otherwisenoted, “NAFION®” NR 005, a “NAFION®” solution available from DuPontNafion® Products, Fayetteville, N.C., and also known as “NAFION®”SE-5110, and is prepared from resin which is approximately 6.3 (TFE)molecules for every perfluoroperfluoro(3,6-dioxa-4-methyl-7-octenesulfonyl fluoride) molecule(CF₂═CF—O—[CF₂CF(CF₃)]—O—CF₂CF₂—SO₂F (PSEPVE)) and has an equivalentweight of approximately 1070. “NAFION®” NR50 PFIEP, the same resin usedto prepared the NR005 (SE-5110) solution is available in pellet formfrom E. I. du Pont de Nemours and Company, Wilmington, Del. (distributedby Aldrich Chemical Company). “NAFION®” NR55 PFIEP is similarlyavailable and structured with carboxylic ends as well as sulfonated endson the pendant groups. “AMBERLYST 15®” sulfonated resin is a registeredtrademark of Rohm and Haas, Philadelphia, Pa. and is sold commerciallyby Rohm and Haas.

Example 1 Preparation of a 40 wt % “NAFION®”/60 wt % Silica Composite

[0081] To 200 mL of a “NAFION®” perfluorinated resin solution (whichconsists of 5 wt % “NAFION®” PFIEP in a mixture of lower alcohols andwater) was added 25 g of a 0.4 M NaOH and the solution was stirred.Separately, in another beaker, to 34 g of tetramethoxy silane[Si(OCH₃)₄] was added 5.44 g of distilled water and 0.5 g of 0.04 M HCland the solution rapidly stirred for 10 minutes. After 10 minutes thesilicon containing solution was added to the rapidly stirring “NAFION®”solution and stirring was continued for about 10 seconds to ensure goodmixing. The solution was left to stand. It was observed that the wholesolution formed a gel within a few seconds (typically 15 sec to 1minute). The gel was covered and left to stand for 24 hours after whichtine the cover was removed and the gel was placed in an oven at 90° C.with a slow stream of nitrogen flushing through the oven. The gel wasleft to dry for 15 hours. The resultant dry glass-like pieces were thenfurther dried at 140° C. under vacuum for 15 hours. The resultantmaterial was re-acidified with HCl as follows, to convert theperfluorosulfonic acid into the acidic, active form. The dried materialwas placed in 100 mL of 3.5 M HCl and the mixture stirred for 1 hour.The HCl solution was removed via filtration and the solid resuspended in100 mL of 3.5 M HCl and stirred for a further hour. The filtering andacidification step was repeated a total of five times. Finally, thesolid was placed in distilled deionized water (200 mL) and stirred for 1hour, filtered and resuspended in water (200 mL) and stirred in order toremove the excess HCl. The solid was filtered and dried at 140° C. for24 hours. The yield was about 22 g. The final material was a finelyparticulate glass-like material with a light yellow coloration. Thecontent of the “NAFION®” PFIEP was about 40 wt %. The solid had a hardtexture typical of sol-gel derived silica type materials with somepieces up to a few nun in size. The material was highly porous with asurface area of 200 m² per gram (BET surface area), a single point porevolume of 0.38 cc/g and an average pore diameter of 5.59 nm.

Example 2 Preparation of a 40 wt % “NAFION®” PFIEP/60 wt % SilicaComposite

[0082] To 200 mL of a “NAFION®” perfluorinated resin solution (whichconsists of 5 wt % “NAFION®” PFIEP in a mixture of lower alcohols andwater) was added 25 g of a 0.4 M NaOH and the solution stirred.Separately, in another beaker, to 34 g of tetramethoxy silane[Si(OCH₃)₄] was added 5.44 g of distilled water and 0.5 g of 0.04 M HCland the solution rapidly stirred for 10 minutes. After 10 minutes thesilicon containing solution was added to the rapidly stirring “NAFION®”solution and stirring was continued for about 10 seconds to ensure goodmixing. The solution was left to stand; it was observed that the wholesolution formed a gel within a few seconds (typically 15 sec to 1minute). The gel was covered and left to stand in an oven at 75° C. for8 hours at which time the cover was removed and the gel was placed in anoven at 90° C. with a slow stream of nitrogen flushing through the oven.The gel was left to dry for 15 hours. The resultant dry glass-likepieces were then further dried at 140° C. under vacuum for 15 hours. Theresultant material was re-acidified with HCl as follows, to convert theperfluorosulfonic acid into the acidic, active form. The dried materialwas placed in 100 mL of 3.5 M HCl and the mixture stirred for 1 hour.The HCl solution was removed via filtration and the solid resuspended in100 mL of 3.5 M HCl and stirred for a further hour. The filtering andacidification step was repeated a total of five times. Finally the solidwas placed in distilled deionized water (200 mL) and stirred for 1 hour,filtered and resuspended in water (200 mL) and stirred in order toremove the excess HCl. The solid was filtered and dried at 140° C. for24 hours. The yield was about 22 g. The final material was a glass likematerial with a light yellow coloration. The content of the “NAFION®”PFIEP was about 40 wt %. The solid had a hard texture typical of sol-gelderived silica type materials. The material was highly porous with asurface area of 131 m² per gram (BET surface area), a single point porevolume of 0.36 cc/g and an average pore diameter of 8.3 nm.

Example 3 Preparation of a 40 wt % “NAFION®” PFIEP/60 wt % SilicaComposite

[0083] To 100 mL of a “NAFION®” perfluorinated resin solution (whichconsists of 5 wt % “NAFION®” PFIEP in a mixture of lower alcohols andwater) was added 15 g of a 0.4 M NaOH and the solution stirred. 17 g oftetramethoxy silane was added to the rapidly stirring “NAFION®” solutionand stirring was continued for about 10 seconds to ensure good mixing.The solution was left to stand; it was observed that the whole solutionformed a gel within about a minute. The gel was covered and placed in anoven at 75° C. for 8 hours after which point the cover was removed andthe gel was placed in an oven at 75° C. with a slow stream of nitrogenflushing through the oven. The gel was left to dry for 15 hours. Theresultant dry glass-like pieces were then further dried at 140° C. underhouse vacuum for 15 hours. The resultant material was re-acidified withHCl as follows, to convert the perfluorosulfonic acid into the acidic,active form. The dried material was placed in 75 mL of 3.5 M HCl and themixture stirred for 1 hour. The HCl solution was removed via filtrationand the solid resuspended in 75 mL of 3.5 M HCl and stirred for afurther hour. The filtering and acidification step was repeated a totalof five times. Finally the solid was placed in distilled deionized water(100 mL) and stirred for 1 hour, filtered and resuspended in water (100mL) and stirred in order to remove the excess HCl. The solid wasfiltered and dried at 140° C. for 24 hours. The yield was about 11 g.The final material was a glass-like material with a light yellowcoloration. The content of the “NAFION®” PFIEP was 40 wt %. The solidhad a hard texture typical of sol-gel derived silica type materials. Thematerial is highly porous with a surface area of 134 m² per gram (BETsurface area), a single point pore volume of 0.37 cc/g and an averagepore diameter of 8.2 nm.

Example 4 Preparation of a 40 wt % “NAFION®” PFIEP/60 wt % SilicaComposite

[0084] To 200 mL of a “NAFION®” perfluorinated resin solution (whichconsists of 5 wt % “NAFION®” PFIEP in a mixture of lower alcohols andwater) was added 17 g of a 0.4 M NaOH and the solution stirred.Separately, in another beaker to 34 g of tetramethoxy silane [Si(OCH₃)₄]was added 5.44 g of distilled water and 0.5 g of 0.04 M HCl and thesolution rapidly stirred for minutes. After 10 minutes the siliconcontaining solution was added to the rapidly stirring “NAFION®” solutionand stirring was continued for about 10 seconds to ensure good mixing.The solution was left to stand; it was observed that the whole solutionformed a gel within a few seconds (typically sec to 2 min). The gel wascovered and left to stand for 24 hours after which point the cover wasremoved and the gel was placed in an oven at 90° C. with a slow streamof nitrogen flushing through the oven. The gel was left to dry forhours. The resultant dry glass-like pieces were then further dried at140° C. under house vacuum for 15 hours. The resultant material wasreacidified with HCl as follows, to convert the perfluorosulfonic acidinto the acidic, active form. The dried material was placed in 100 mL of3.5 M HCl and the mixture stirred for 1 hour. The HCl solution wasremoved via filtration and the solid resuspended in 100 mL of 3.5 M HCland stirred for a further hour. The filtering and acidification step wasrepeated a total of five times. Finally the solid was placed indistilled deionized water (200 mL) and stirred for 1 hour, filtered andresuspended in water (200 mL) and stirred in order to remove the excessHCl. The solid was filtered and dried at 140° C. for 24 hours. The yieldwas about 22 g. The final material was a glass-like material with alight yellow coloration. The content of the “NAFION®” PFIEP was 40 wt %.The solid had a hard texture typical of sol-gel derived silica typematerials with some pieces up to a few mm in size. The material washighly porous with a surface area of 294 m² per gram (BET surface area),a single point pore volume of 0.30 cc/g and an average pore diameter of3.5 nm.

Example 5 Preparation of a ca. 20 wt % “NAFION®” PFIEP/80 wt % SilicaComposite

[0085] To 100 mL of a “NAFION®” perfluorinated resin solution (whichconsists of 5 wt % “NAFION®” PFIEP in a mixture of lower alcohols andwater) was added 25 g of a 0.4 M NaOH and the solution stirred.Separately, in another beaker to 34 g of tetramethoxy silane [Si(OCH₃)₄]was added 5.44 g of distilled water and 0.5 g of 0.04 M HCl and thesolution rapidly stirred for 10 minutes. After 10 minutes the siliconcontaining solution was added to the rapidly stirring “NAFION®” solutionand stirring was continued for about seconds to ensure good mixing. Thesolution was left to stand; it was observed that the whole solutionformed a gel within a few seconds (typically 15 sec to 1 min). The gelwas covered and left to stand for 24 hours after which point the coverwas removed and the gel was placed in an oven at 90° C. with a slowstream of nitrogen flushing through the oven. The gel was left to dryfor hours. The resultant dry glass-like pieces were then further driedat 140° C. under house vacuum for 15 hours. The resultant material wasreacidified with HCl as follows, to convert the perfluorosulfonic acidinto the acidic, active form. The dried material was placed in 100 mL of3.5 M HCl and the mixture stirred for 1 hour. The HCl solution wasremoved via filtration and the solid resuspended in 100 mL of 3.5 M HCland stirred for a further hour. The filtering and acidification step wasrepeated a total of five times. Finally the solid was placed indistilled deionized water (200 mL) and stirred for 1 hour, filtered andresuspended in water (200 mL) and stirred in order to remove the excessHCl. The solid was filtered and dried at 125° C. for 24 hours. The finalmaterial was a glass-like material with a light yellow coloration. Thecontent of the “NAFION®” PFIEP was about 20 wt %. The solid had a hardtexture typical of sol-gel derived silica type materials. The materialwas highly porous with a surface area of 287 m² per gram (BET surfacearea), a single point pore volume of 0.63 cc/g and an average porediameter of 6.70 nm.

Example 6 Preparation of a ca. 10 wt % “NAFION®”/90 wt % SilicaComposite

[0086] To 50 mL of a “NAFION®” perfluorinated resin solution (whichconsists of 5 wt % “NAFION®” PFIEP in a mixture of lower alcohols andwater) was added 25 g of a 0.4 M NaOH and the solution stirred.Separately, in another beaker to 34 g of tetramethoxy silane [Si(OCH₃)₄]was added 5.44 g of distilled water and 0.5 g of 0.04 M HCl and thesolution rapidly stirred for 10 minutes. After 10 minutes the siliconcontaining solution was added to the rapidly stirring “NAFION®” solutionand stirring was continued for about 10 seconds to ensure good mixing.The solution was left to stand; it was observed that the whole solutionformed a gel within a few seconds (typically 15 sec to 1 min). The gelwas covered and left to stand for 24 hours after which point the coverwas removed and the gel was placed in an oven at 90° C. with a slowstream of nitrogen flushing through the oven. The gel was left to dryfor 15 hours. The resultant dry glass-like pieces were then furtherdried at 140° C. under house vacuum for 15 hours. The resultant materialwas reacidified with HCl as follows, to convert the perfluorosulfonicacid into the acidic, active form. The dried material was placed in 100mL of 3.5 M HCl and the mixture stirred for 1 hour. The HCl solution wasremoved via filtration and the solid resuspended in 100 mL of 3.5 M HCland stirred for a further hour. The filtering and acidification step wasrepeated a total of five times. Finally the solid was placed indistilled deionized water (200 mL) and stirred for 1 hour, filtered andresuspended in water (200 mL) and stirred in order to remove the excessHCl. The solid was filtered and dried at 125° C. for 24 hours. The finalmaterial was a glass like material with a light yellow coloration. Thecontent of the “NAFION®” PFIEP was about 10 wt %. The solid had a hardtexture typical of sol-gel derived silica type materials. The materialwas highly porous with a surface area of 270 m² per gram (BET surfacearea), a single point pore volume of 0.59 cc/g and an average porediameter of 6.50 nm.

Example 7 Preparation of “NAFION®” PFIEP 40 wt % and Silica 60 wt % withDual Porosity Having both Large (ca. 500 nm) and Small (ca. 2-15 nm)Pores

[0087] To 100 mL of the “NAFION®” solution (which consists of 5 wt %“NAFION®” PFIEP in a mixture of lower alcohols and water) was added 15 gof a 0.4 M NaOH and the solution stirred. 4 g of calcium carbonate(Albafil Specialty Minerals, Adams, Mass. with a particle size of about0.5 microns) was added to the basic “NAFION®” and calcium carbonatemixture which was ultrasonicated for 1 minute to 10 minutes using asonic probe (Heat Systems Inc., Farmingdale, N.Y.). Separately, inanother beaker to 17 g of tetramethoxy silane [Si(OCH₃)₄] was added 2.7g of distilled water and 0.25 g of 0.04 M HCl and the solution rapidlystirred for 10 minutes. After 10 minutes the silicon containing solutionwas added to the rapidly stirring “NAFION®” solution and stirring wascontinued for about 10 seconds to ensure good mixing. The solution wasleft to stand; it was observed that the whole solution formed a gelwithin a few seconds (typically 10 sec to 1 min). The gel was coveredand left to stand for 4 hours after which point the cover was removedand the gel was placed in an oven at 90° C. with a slow stream ofnitrogen flushing through the oven. The gel was left to dry for 15hours. The resultant dry glass-like pieces were then further dried at140° C. under house vacuum for 15 hours. The resultant material wasreacidified with HCl as follows, to convert the perfluorosulfonic acidinto the acidic, active form and also to dissolve out the calciumcarbonate. The dried material was placed in 100 mL of 3.5 M HCl and themixture stirred for 1 hour. Upon addition of the acid a large amount ofgas was evolved (due to the reaction of the acid with HCl). The HClsolution was removed via filtration and the solid resuspended in 100 mLof 3.5 M HCl and stirred for a further hour. The filtering andacidification step was repeated a total of five times. Finally the solidwas placed in distilled deionized water (200 mL) and stirred for 1 hour,filtered and resuspended in water (200 mL) and stirred in order toremove the excess HCl. The solid was filtered and dried at 125° C. for24 hours. The final material was a glass-like material with a lightyellow coloration. The microstructure of the derived material wasinvestigated using scanning electron microscopy. The micrograph clearlyshows very large pores about 0.5-1 micron in size. Also using energydispersive x-ray analysis, no Ca could be detected showing that most ofthe calcium carbonate has been removed upon reacidification. Thematerial was highly porous with a surface area of 310 m² per gram (BETsurface area), and a single point pore volume of 0.46 cc/g.

Example 8 Catalytic Testing of “NAFION®” PFIEP/Silica Composites Usingthe Alkylation of Toluene with n-heptene

[0088] It is well known in the art that solid acid catalysts cancatalyze a range of reactions, for example, alkylation reactions. Wedescribe the use of the silica/“NAFION®” PFIEP composites to catalyzethe alkylation of toluene with n-heptene, and measure the conversion ofheptene and toluene using gas chromatography.

[0089] As a comparison we also tested the catalytic activity of the“NAFION®” PFIEP itself which is available in pellet form from E. I. duPont de Nemours and Company, Wilmington, Del. 19898 (distributed byAldrich Chemical Company) and is known as “NAFION®” NR 50 PFIEP.

[0090] A typical reaction is described as follows.

[0091] Both toluene and heptene were dried over 3A molecular sievebefore use (dried for 24-hours). In a round bottom flask was added 15.6g of toluene and 8.4 g of n-heptene, and a “TEFLON®” coated magneticstirrer added. A reflux condenser was attached to the flask and a slowstream of nitrogen passed over the top of the reflux condenser tominimize moisture. The flask and contents were heated to 100° C. Asample of 1 gram of the “NAFION®” PFIEP/silica catalyst (which is madeup of 40 wt % “NAFION®” PFIEP and 60 wt % silica) as described inExample 1 was gently ground to break down the large pieces (to give amaterial about 0.1 to 1 mm in size) and the solid dried in vacuum at140° C. for 24 hours. The dried material was added to thetoluene/n-heptene mixture and the solution stirred and left to react forexactly 2 hours. After 2 hours a sample was removed and the conversionof heptene was measured using gas chromatography. In the GC analysisdodecane was used as a standard. The conversion of heptene was measuredto be 90% to 95%, leaving only 10% to 5% of the heptene unreacted.

[0092] As a comparison experiment, the catalytic activity of 0.4 g of“NAFION®” NR 50 PFIEP was tested. 0.4 g represents the same weight of“NAFION®” PFIEP as tested above for the composite. The exact sameprocedure was used, drying the “NAFION®” NR 50 PFIEP at 140° C. for 24hours and adding the “NAFION®” NR 50 PFIEP to the stirred solution oftoluene (15.6 g) and heptene (8.4 g) at 100° C. After 2 hour reactiontime the conversion was found to be about 3%, leaving 97% of the hepteneunreacted.

Example 9

[0093] The procedure as described in Example 7 was carried out exactlyexcept in this case a 20 wt % “NAFION®” PFIEP/80 wt % silica compositewas evaluated for catalytic activity, prepared as described in Example4. Using 1 g of catalyst (and 15.6 g toluene and 8.4 heptene) lead to aconversion of heptene of 79%. As a comparison, using 0.2 g of NR 50 leadto a conversion of between 1-2%.

Example 10

[0094] The procedure as described in Example 7 was carried out exactlyexcept in this case a 10 wt % “NAFION®” PFIEP/90 wt % silica compositewas evaluated for catalytic activity, prepared as described in Example5. Using 1 g of catalyst (and 15.6 g toluene and 8.4 heptene) lead to aconversion of heptene of 75%. As a comparison, using an equivalentweight of 0.1 g of NR 50 lead to a conversion of less than 1% leavingmore than 99% of the heptene unreacted.

Example 11 Preparation of a 40 wt % “NAFION®” PFIEP/60 wt % SilicaComposite Using Sodium Silicate as the Silica Source

[0095] 150 mL of a 9% sodium silicate solution, which was made up bytaking 45.6 mL of a sodium silicate solution (which contained 29.6% ofsilica) in SiO₂ and adding sufficient distilled water to bring thevolume up to 150 mL. The measured pH was about 12.5. The solution wascooled to about 10° C. using an ice bath. The solution was stirred andan DOWEX® cation exchange resin was added until the pH reached 2.5, overabout 2-3 minutes. This process generated polysilicic acid. The solutionwas separated from the resin by filtration. 35 mL of a 5% “NAFION®”PFIEP in alcohol/water mixture was added to the above solution withrapid stirring and the stirrer was stopped after about 1 min. Thesolution was covered and placed in an oven for 17 h at 90° C., afterwhich point the whole system formed a solid gel. The cover was removedand the material was dried in an oven at 90° C. for 24 hours, andfinally dried under vacuum at 140° C. for 17 h. This yielded hard, glasslike pieces, which are typical of silica gel, with sizes in the range ofabout 0.1 to 5 mm. The dried glass was reacidified in 3.5 M HCl (ca. 100mL of acid), and was stirred and filtered and the process repeated fivetimes. Finally the material was washed by stirring with water (100 mL)and filtering and repeating the process 2 times. The reacidifiedmaterial was dried at 140° C. for 17 h, which yielded a glass like,slightly brown, “NAFION®” PFIEP/silica composite.

Catalytic Testing

[0096] Both toluene and n-heptene were dried over 3A molecular sievebefore use (dried for 24 hours). In a round bottom flask was added 15.6g of toluene and 8.4 g of n-heptene, and a “TEFLON®” coated magneticstirrer added. A reflux condenser was attached to the flask and a slowstream of nitrogen passed over the top of the reflux condenser tominimize moisture. The flask and contents were heated to 100° C. Asample of 1 gram of the “NAFION®” PFIEP/silica catalyst (which was madeup of 10 wt % “NAFION®” PFIEP and 90 wt % silica) as described above wasgently ground to break down the large pieces (to give a material about0.1 to 1 mm in size) and the solid dried in vacuum at 140° C. for 24hours. The dried material was added to the toluene/n-heptene mixture andthe solution stirred and left to react for exactly 2 hours at 100° C.After 2 hours a sample was removed and the conversion of n-heptene wasmeasured using gas chromatography. In the GC analysis dodecane was usedas a standard. The conversion of heptene was measured to be 36%.

Example 12 Preparation of a 20 wt % “NAFION®” PFIEP/80 wt % AluminaComposite

[0097] 49.2 g of aluminum tri-secbutoxide [Al(OC₄H₉)₃] was added to 362mL of distilled water at 75° C. and the mixture was left to stir for 15min. To the stirred solution was added 1.36 g of a 69% concentratednitric acid solution and the material was transfered to a sealed jar,and left in an oven at 90° C. for 24 h. A free flowing aluminumcontaining solution resulted. The formation of alumina gels that formporous transparent alumina has been described by B. E. Yoldas, in J.Mat. Sci 10 (1975) 1856 and B. E. Yoldas, Ceramics Bulletin, 54 (1975)289. To 200 mL of the above solution was added 20 mL of a 5% “NAFIO®”PFIEP containing alcohol/water resin solution. The material was stirredon a hot plate with a solution temperature of 80° C. until all of thesolvent evaporated, leaving a glass-like solid. The glass-like solid hadparticles in the range of about 0.1 to 2 mm. The material containedabout 20 wt % “NAFION®” PFIEP and 80 wt % alumina. The material wasreacidified with 4M HCl in dioxane.

Example 13 13.5 wt. % “NAFION®” PFIEP in Silica, with Pore Diameter ca.10 nm

[0098] 204 g of tetramethoxysilane (TMOS), 33 g of distilled water and 3g of 0.04M HCl was stirred for 45 mins. to give a clear solution. To 300mL of a “NAFION®” solution (which contains 5% of “NAFION®” PFIEP byweight) was added 150 mL of a 0.4M NaOH solution, while the “NAFION®”solution was being stirred. After addition of the sodium hydroxidesolution the resulting solution was stirred for a further 15 min. Thesilicon containing solution, prepared as described above, was addedrapidly to the stirred “NAFION®” containing solution. After about 10-15seconds the solution gelled to a solid mass. The gel was placed in anoven and dried at a temperature of about 95° C., over a period of about2 days, followed by drying under vacuum overnight. The hard glass-likeproduct was ground and passed through a 10-mesh screen. The material wasthen stirred with 3.5M HCl for 1 hour (with 500 mL of acid), followed bywashing with 500 mL of deionized water. The solid was collected byfiltration. Acidification, washing and filtration were repeated a totalof 5 times and after the final wash the solid was dried under vacuum at100° C. for 24 hours. Yield of dried product was 98 g. The surface area(determined by BET), pore volume and pore diameter was determined to be344 m²/g, 0.85 cc/g and 9.8 nm, respectively.

Example 14 40 wt. % “NAFION®” PFIEP in Silica, with Pore Diameter ca. 10nm

[0099] 204 g of tetramethoxysilane (TMOS), 33 g of distilled water and 3g of 0.04M HCl was stirred for 45 mins. to give a clear solution. To1200 mL of a “NAFION®” solution (which contains 5% of “NAFION®” PFIEP byweight) was added 150 ml of a 0.4M NaOH solution, while the “NAFION®”solution was being stirred. After addition of the sodium hydroxidesolution, the resulting solution was stirred for a further 15 min. Thesilicon containing solution, prepared as described above, was addedrapidly to the stirred “NAFION®” containing solution. After about 10-15seconds the solution gelled to a solid mass. The gel was placed in anoven and dried at a temperature of about 95° C., over a period of about2 days, followed by drying under vacuum overnight. The hard glass-likeproduct was ground and passed through a 10-mesh screen. The material wasthen stirred with 3.5M HCl for 1 hour (with 500 mL of acid) followed bywashing with 500 mL of deionized water. The solid was collected byfiltration. Acidification, washing and filtration were repeated a totalof 5 times and after the final wash the solid was dried under vacuum at100° C. for 24 h. Yield of dried product was 130 g. The surface area(determined by BET), pore volume and pore diameter was determined to be468 m²/g, 1.05 cc/g and 8.9 nm, respectively.

Example 15 8 wt. % “NAFION®” PFIEP in Silica, with Pore Diameter ca. 10nm

[0100] 204 g of tetramethoxysilane (TMOS), 33 g of distilled water and 3g of 0.04M HCl was stirred for 45 mins. to give a clear solution. To 150mL of a “NAFION®” solution (which contains 5% of “NAFION®” PFIEP byweight) was added 150 mL of a 0.4M NaOH solution, while the “NAFION®”solution was being stirred. The sodium hydroxide was added over about 1min. After addition of the sodium hydroxide solution, the resultingsolution was stirred for a further 15 min. The silicon containingsolution, prepared as described above, was added rapidly to the stirred“NAFION®” containing solution. After about 10-15 seconds the solutiongelled to a solid mass. The gel was placed in an oven and dried at atemperature of about 95° C., over a period of about 2 days, followed bydrying under vacuum overnight. The hard glass-like product was groundand passed through a 10-mesh screen. The material was then stirred with3.5M HCl for 1 hour (with 500 mL of acid), followed by washing with 500mL of deionized water. The solid was collected by filtration.Acidification, washing and filtration were repeated a total of 5 timesand after the final wash the solid was dried under vacuum at 100° C. for24 h. Yield of dried product was 82 g. The surface area (determined byBET), pore volume and pore diameter was determined to be 412 m²/g, 0.84cc/g and 10.3 nm, respectively.

Example 16 13 wt. % “NAFION®” PFIEP in Silica, with Pore Diameter ca. 20nm

[0101] 204 g of tetramethoxysilane (TMOS), 33 g of distilled water and 3g of 0.04M HCl was stirred for 45 mins. to give a clear solution. To 300mL of a “NAFION®” solution (which contains 5% of “NAFION®” PFIEP byweight) was added 150 mL of a 0.8M NaOH solution, while the “NAFION®”solution was being stirred. After addition of the sodium hydroxidesolution the resulting solution was stirred for a further 15 min. Boththe silicon containing solution and the “NAFION®” containing solutionwere cooled in ice to lower the solution temperature to about 10° C. Thesilicon containing solution, prepared as described above, was addedrapidly to the stirred “NAFION®” containing solution. After about 10seconds the solution gelled to a solid mass. The gel was placed in anoven and dried at a temperature of about 90° C., over a period of about2 days, followed by drying under vacuum overnight. The hard glass-likeproduct was ground and passed through a 10-mesh screen. The material wasthen stirred with 3.5M HCl for 1 hour (with 500 mL of acid) followed bywashing with 500 mL of deionized water. The solid was collected byfiltration. Acidification, washing and filtration were repeated a totalof 5 times and after the final wash the solid was dried under vacuum at100° C. for 24 h. Yield of dried product was 97 g. The surface area(determined by BET), pore volume and pore diameter was determined to be123 m²/g, 0.84 cc/g and 22 nm, respectively.

Example 17 40 wt. % “NAFION®” PFIEP in Silica, with both Small ca. 10 nmand Large ca. 0.5 μm Sized Pores, Dual Porosity Gels

[0102] 255 g of tetramethoxysilane (TMOS), 40.75 g of distilled waterand 3.75 g of 0.04M HCl was stirred for 45 mins. to give a clearsolution. To 1500 mL of a “NAFION®” solution (which contains 5% of“NAFION®” PFIEP by weight) was added 187 mL of a 0.4M NaOH solution,while the Nafion solution was being stirred, followed by 187 g ofcalcium carbonate (supplied by Albafil Specialty Minerals). Afteraddition of the sodium hydroxide solution, the resulting solution wassonicated for a further 15 min. using a Branson ultrasonic probe toensure dispersion of the calcium carbonate. The silicon containingsolution, prepared as described above, was added rapidly to the stirred“NAFION®” containing solution. After about 10-15 seconds the solutiongelled to a solid mass. The gel was placed in an oven and dried at atemperature of about 95° C., over a period of about 2 days, followed bydrying under vacuum overnight. The hard glass-like-product was groundand passed through a 10-mesh screen. The material was then stirred with3.5M HCl for 1 hour (with 500 mL of acid), followed by washing with 500mL of deionized water. The solid was collected by filtration.Acidification, washing, and filtration were repeated a total of 5 timesand after the final wash the solid was dried under vacuum at 100° C. for24 h. Yield of dried product was 168 g. The surface area (determined byBET), pore volume and pore diameter was determined to be 57 m²/g, 0.21cc/g and 13 nm, respectively.

Example 18 13 wt. % “NAFION®” PFIEP in Silica, with Pore Diameter ca.2.1 nm

[0103] 204 g of tetramethoxysilane (TMOS), 33 g of distilled water and 3g of 0.04M HCl was stirred for 30 mins. to give a clear solution. To 300mL of a “NAFION®” solution, HCl was added to yield an HCl concentrationof 0.01M. The silicon containing solution, prepared as described above,was added rapidly to the stirred “NAFION®” containing solution. Thevessel was sealed and placed in a heated oven overnight at 65° C., afterwhich point the system gelled. The top was removed and the flask andcontents were placed in an oven and dried at a temperature of about 95°C., over a period of about 2 days, followed by drying under vacuumovernight. The hard glass-like product was ground and passed through a10-mesh screen. The material was then stirred with 3.5M HCl for 1 hour(with 500 mL of acid), followed by washing with 500 mL of deionizedwater. The solid was collected by filtration. Acidification, washing andfiltration were repeated a total of 5 times and after the final wash thesolid was dried under vacuum at 100° C. for 24 h. Yield of dried productwas 96 g. The surface area (determined by BET), pore volume and porediameter was determined to be 563 m²/g, 0.15 cc/g and 2.1 nm,respectively.

Example 19 42 wt. % “NAFION®” PFIEP in Silica, No Acid Hydrolysis Stepvia TMOS

[0104] 15 g of 0.4M NaOH was added to 100 mL of a 5% “NAFION®” solution.To this solution was added 17 g of TMOS and the solution gelled within15 secs. The solid gel was dried at 95° C. in an oven vented withflowing nitrogen, for 2 days, followed by vacuum drying at 140° C. Thesolid was reacidified with 3.5M HCl for 1 hour (with 50 mL of acid),followed by washing with 50 mL of de-ionized water. The solid wascollected by filtration. Acidification, washing and filtration wererepeated a total of 5 times and after the final wash the solid was driedunder vacuum at 100° C. for 24 h. Yield of dried product was 9 g. Thesurface area (determined by BET), pore volume and pore diameter wasdetermined to be 330 m²/g, 0.36 cc/g and 8.3 nm, respectively.

Example 20 8 wt. % “NAFION®” in Silica, Adding Silica to “NAFION®”, thenthe NaOH

[0105] 20.4 g of TMOS, 3.2 g of water and 0.2 g of 0.04M HCl was stirredfor 30 min. and added to 15 mL of 5% “NAFION®” solution with rapidstirring. To the silica and “NAFION®” containing solution, 15 g of 0.4MNaOH was rapidly added while the solution was rapidly stirred. Thesolution turned to a solid gel within about 10 seconds. The gel wasdried at 98° C. for 2 days followed by drying under vacuum overnight at100° C. The solid was re-acidified with 3.5M HCl for 1 hour (with 150 mLof acid), followed by washing with 50 mL of de-ionized water. The solidwas collected by filtration. Acidification, washing and filtration wererepeated a total of 5 times and after the final wash the solid was driedunder vacuum at 100° C. for 24 h. Yield of dried product was 9 g. Thesurface area (determined by BET), pore volume and pore diameter wasdetermined to be 364 m²/g, 1.06 cc/g and 11.5 nm, respectively.

Example 21 “NAFION®” PFIEP/Silica Composite via Tetraethoxysilane

[0106] 108 g of tetraethoxysilane, 28.8 g of water and 2.4 g of 0.04MHCl was stirred for 2.5 hours to give a clear solution. 55 mL of 0.4MNaOH was added to 75 mL of stirred “NAFION®” solution (5%) and thestirring continued for 15 mins. The silica solution was rapidly added tothe stirring “NAFION®” solution and the system formed a gel within 10-15seconds. The gel was dried at 95° C. for two days followed by vacuumdrying at-125° C. overnight. The gel was ground and passed through a10-mesh screen and re-acidified with 3.5M HCl for 1 hour (with 250 mL ofacid), followed by washing with 250 mL of de-ionized water. The solidwas collected by filtration. Acidification, washing and filtration wererepeated a total of 5 times and after the final wash the solid was driedunder vacuum at 100° C. for 24 h. Yield of dried product was 32 g. Thesurface area (determined by BET), pore volume and pore diameter wasdetermined to be 330 m²/g, 0.75 cc/g and 7.5 nm, respectively.

Example 22 “NAFION®” PFIEP/Silica Composite via Sodium Silicate Solution

[0107] To 100 g of sodium silicate solution (which contained 29% byweight of silica), was added 210 mL of water. To this solution 300 g ofDOWEX® cation exchange resin was very quickly added and stirred rapidlyuntil the pH dropped to about 3 (in less than 2 minutes). The solutionwas filtered. 30 mL of a 5% “NAFlON®” solution was added to 150 mL ofthe filtrate while it was stirred. 5 mL of 2M NaOH was then added andthe solution gelled; pH was close to 6.0. The gel was dried at 95° C.for two days and then dried under vacuum at 100° C. for 1 day. The gelwas ground and passed through a 10-mesh screen and re-acidified with3.5M HCl for 1 hour (with 250 mL of acid), followed by washing with 250mL of de-ionized water. The solid was collected by filtration.Acidification, washing and filtration were repeated a total of 5 timesand after the final wash the solid was dried under vacuum at 100° C. for24 h. Yield of dried product was 15.6 g. The surface area (determined byBET), pore volume and pore diameter was determined to be 350 m²/g, 0.74cc/g and 7.1 mm, respectively.

Example 23 6 wt. % “NAFION®” PFIEP in Silica, Using Sodium SilicateSolution

[0108] 50 g of distilled water was added to 20 g of a sodium silicatesolution (which contained 29% by weight of silica). 10 g of a 5%“NAFION®” solution was added with rapid stirring. The solution was addeddropwise over about 10 mins. Next, 24 mL of a 12.41% HCl solution wasadded while rapidly stirring, and the pH dropped to 1.8. Next, 0.4M NaOHwas added rapidly to adjust the pH to 6, after which point the solutionformed a gel. The gel was ground and passed through a 10-mesh screen andre-acidified with 3.5M HCl for 1 hour (with 100 mL of acid), followed bywashing with 100 mL of de-ionized water. The solid was collected byfiltration. Acidification, washing and filtration were repeated a totalof 5 times and after the final wash the solid was dried under vacuum at100° C. for 24 h. Yield of dried product was 6.5 g. The surface area(determined by BET), pore volume and pore diameter was determined to be387 m²/g, 0.81 cc/g and 7.1 nm, respectively.

Example 24 10 wt. % “NAFION®” PFIEP in Silica via “LUDOX®” 40 ColloidalSilica

[0109] 200 mL of “LUDOX®” 40 (which contains 80 g of silica) was addedto 160 mL of 5% “NAFION®” solution. The pH was adjusted to 6.0 using3.5M HCl. The solution was placed in a sealed glass vessel and placed inan oven at 60-70° C. After 1 hour the system gelled. The material wasdried at 90° C., followed by vacuum drying at 140° C. The gel wasreacidified with 3.5M HCl for 1 hour (with 500 mL of acid), followed bywashing with 500 mL of de-ionized water. The solid was collected byfiltration. Acidification, washing and filtration were repeated a totalof 5 times and after the final wash the solid was dried under vacuum at100° C. for 24 h.

Example 25 A Composite of “NAFION®” (NR55) PFIEP in Silica

[0110] 150 mL of a 5% solution of “NAFION®” (NR55, which contains bothsulfonic acid and carboxylic acid groups), was added to 60 mL ofisopropanol, 15 mL of methanol, and 75 mL of water. To this was added150 g of 0.4M NaOH. Separately, 204 g of TMOS, 32.6 g of water and 3 gof 0.04M HCl was stirred for 20 mins and then added to the NR55solution. The gel that formed was dried at 100° C. over 24 hrs, groundand passed through a 10-mesh screen. The material was then stirred with3.5M HCl for 1 hour (with 500 mL of acid), followed by washing with 500ml of de-ionized water. The solid was collected by filtration.Acidification, washing and filtration were repeated a total of 5 timesand after the final wash the solid was dried under vacuum at 100° C. for24 h. Yield of dried product was 92.6 g. The “NAFION®” PFIEP content was7.5 wt %.

Example 26 “NAFION®” PFIEP Entrapped in Si—Al—Zr Composite

[0111] 20.4 g of TMOS, 3.6 g of water and 0.3 g of 0.04M HCl was stirredfor 20 mins. and added to 5 g of the mixed aluminum/zirconium complex(Al₂Zr(OR)_(x) available from Gelest, Tullytown, Pa. The mixture wasstirred for 5 mins. 30 g of 5% “NAFION®” solution and 15 g of 0.4M NaOHwere mixed and added to the Si—Al—Zr containing solution, and thematerial was placed in an oven at 75° C. and dried at 100° C.

Example 27 Nitric Acid Treatment of Used or Organic ContaminatedComposites

[0112] The above described materials of the present invention are usedfor a range of catalytic reactions. For some reactions, some browncoloration may form upon the catalyst. Catalysts can be regenerated bytreatment with acid. 100 g of 13 wt. % “NAFION®” PFIEP in silica wasmixed with 1 liter of 35% nitric acid and the solid stirred at 75° C.overnight. The white solid obtained was washed with de-ionized water toremove excess acid and was dried at 100° C. under vacuum overnight.

Example 28 Catalytic Testing of “NAFION®” PFIEP/Silica Composites Usingthe Alkylation of Toluene with n-heptene

[0113] It is well known in the art that solid acid catalysts cancatalyze a range of reactions, for example, alkylation reactions. Thesilica/“NAFION®” PFIEP composites of the present invention can be usedto catalyze the alkylation of toluene with n-heptene, measuring theconversion of n-heptene using gas chromatography.

[0114] As a comparison, the catalytic activity of “NAFION®” PFIEP itselfwhich is available in pellet form from E. I. du Pont de Nemours andCompany, Wilmington, Del., and is known as “NAFION®” NR 50, was alsotested.

Illustrative Example of Present Invention

[0115] Both toluene and n-heptene were dried over 3A molecular sievebefore use (dried for 24 hours). In a round bottom flask was added 15.6g of toluene and 8.4 g of n-heptene, and a Teflon coated magneticstirrer added. A reflux condenser was attached to the flask and a slowstream of nitrogen passed over the top of the reflux condenser tominimize moisture. The flask and contents were heated to 100° C. Asample of 1 g of the “NAFION®” PFIEP/silica catalyst as described inExample 14 was dried in vacuum at 150° C. for 15 hours. The driedmaterial was added to the toluene/n-heptene mixture and the solutionstirred and left to react for exactly 2 hours. After two hours a samplewas removed and the conversion of n-heptene was measured using gaschromatography. In the GC analysis dodecane was used as a standard. Theconversion of n-heptene was measured to be 98%, leaving only 2% of theheptene unreacted.

Comparative Example

[0116] As a comparison experiment, the catalytic activity of 0.4 g of“NAFION®” NR50 PFIEP was tested. 0.4 g represents the same weight of“NAFION®” PFIEP as tested above for the composite of the presentinvention. The exact same procedure was used, drying the NR50 at 150° C.for 24 hours and adding the NR50 to the stirred solution of toluene(15.6 g) and heptene (8.4 g) at 100° C. After 2 hour reaction time theconversion was found to be about 3%, leaving 97% of the hepteneunreacted.

Example 29

[0117] The illustrative example as described in Example 28 was carriedout with the exception that 1 g of the material from Example 13 was usedin the catalysis run. Thus, 1 g of a 13 wt. % Nafion in silica was used.The conversion was found to be 89% of heptene.

[0118] As a comparative example, 0.13 g of “NAFION®” NR50 was used ascatalyst (again with the same conditions as described in Example 28,comparative example). The measured conversion was about 1% of heptene.

Example 30

[0119] The illustrative example as described in Example 28 was carriedout with the exception that 1 g of the material from Example 15 was usedin the catalysis run. The conversion was found to be 84% of heptene.

Example 31

[0120] The illustrative example as described in Example 28 was carriedout with the exception that 1 g of the material from Example 16 was usedin the catalysis run. The conversion was found to be 94% of heptene.

Example 32

[0121] The illustrative example as described in Example 28 was carriedout with the exception that 1 g of the material from Example 17 was usedin the catalysis run. The conversion was found to be 97% of heptene.

Example 33

[0122] The illustrative example as described in Example 28 was carriedout with the exception that 1 g of the material from Example 18 was usedin the catalysis run. The conversion was found to be 91% of heptene.

Example 34

[0123] The illustrative example as described in Example 28 was carriedout with the exception that 1 g of the material from Example 19 was usedin the catalysis run. The conversion was found to be 83% of heptene.

Example 35

[0124] The illustrative example as described in Example 28 was carriedout with the exception that 1 g of the material from Example 20 was usedin the catalysis run. The conversion was found to be 93% of heptene.

Example 36

[0125] The illustrative example as described in Example 28 was carriedout with the exception that 1 g of the material from Example 21 was usedin the catalysis run. The conversion was found to be 86% of heptene.

Example 37

[0126] The illustrative example as described in Example 28 was carriedout with the exception that 1 g of the material from Example 22 was usedin the catalysis run. The conversion was found to be 82% of heptene.

Example 38

[0127] The illustrative example as described in Example 28 was carriedout with the exception that 1 g of the material from Example 23 was usedin the catalysis run. The conversion was found to be 76% of heptene.

Example 39

[0128] The illustrative example as described in Example 28 was carriedout with the exception that 1 g of the material from Example 24 was usedin the catalysis run. The conversion was found at to be 28% of heptene.

Example 40

[0129] The illustrative example as described in Example 28 was carriedout with the exception that 1 g of the material from Example 25 was usedin the catalysis run. The conversion was found to be 64% of heptene.

Example 41 Catalytic Testing of “NAFION®” PFIEP/Silica Composite Usingthe Dimerization of Alpha Methylstyrene (AMS)

[0130] The dimerization of alpha-methylstyrene (AMS) with “NAFION®”PFIEP has been studied in detail in the past (B. Chaudhuri and M. M.Sharme, Ind. Eng. Chem. Res. 1989, 28, 1757-1763). The products of thereaction are a mixture of the individual unsaturated dimers(2,4-diphenyl-4-methyl-1-pentene and 2,4-diphenyl-4-methyl-2-pentene)and the saturated dimers (1,1,3-trimethyl-3-phenylindan and cis andtrans-1,3-dimethyl-1,3-diphenylcyclobutane). With “NAFION®” PFIEP as thecatalyst, the reaction was found to be very slow.

Illustrative Example of the Present Invention

[0131] 0.5 g of the solid made via Example 13 was used as catalyst. 5 gof alphamethylstyrene and 45 g of cumene as solvent was heated to 60° C.To this solution 0.5 g of the catalyst was added, and reagents andcatalyst were stirred and heated at 60° C. After 30 mins. the amount ofalphamethylstyrene was measured using GC analysis, which showed aconversion of about 99%, with less than 1% of the reactant AMSremaining. After 200 mins. of reaction time the conversion of AMS wasabout 100%.

Comparative Example

[0132] 0.07 g of 100% “NAFION®” NR50 PFIEP was used as catalyst. 5 g ofalphamethylstyrene and 45 g of cumene as solvent were heated to 60° C.To this solution 0.07 g of the catalyst was added, and reagents andcatalyst were stirred and heated at 60° C. After 30 mins. the amount ofalphamethylstyrene was measured using GC analysis, which showed aconversion of less than 1%, with more than 99% of the reactant AMSremaining. After 200 mins. of reaction time the conversion ofalphamethylstyrene was about 5 with 95% of the AMS unchanged.

Example 42 Catalytic Testing of NAFION®” PFIEP/Silica Composite Usingthe Nitration of Benzene to Form Nitrobenzene

[0133] A 250 mL three necked flask was equipped with a Dean-Starkmoisture trap and a magnetic stirrer. The flask was loaded with 70-75 gbenzene, 10 g MgSO₄ (as a desiccant), 5.0 g 1,3,5-trichlorobenzene(internal standard) and 7.5 g of the appropriate acid catalyst. Themixture was heated to reflux at atmospheric pressure, under inertatmosphere. After about 30 min. at reflux, a feed pump was turned on,and 90% HNO₃ was fed into the reactor at a rate of about 0.06 mL/min.The reaction mixture was maintained at reflux, and samples were removedat 15-30 minute intervals for GC analysis. The average nitric acidconversions and nitrobenzene selectivities, over the 150 min. run timeare given below in Table I: TABLE I % HNO₃ % Selectivity Acid CatalystConversion (nitrobenzene) 13.5% “NAFION ®”/ 82 ± 8 99.6 ± 0.2 silicacomposite (from Example 13) “NAFION ®” 64 ± 8 98.8 ± 1.0 NR50 beads None35 ± 7 97.9 ± 0.6

Example 43 Catalytic Testing of “NAFION®” PFIEP/Silica Composite Usingthe Conversion of Cyclohexene with Acetic Acid to Cyclohexl Acetate

[0134] The esterification of cyclohexene with acetic acid using solidacid catalyst was carried out in liquid phase in a Fisher-Porterreactor. The reactor comprised of a glass tube fitted with a gasinjection port, liquid sampling port, thermocouple, and pressure gauge.Mixing in the reactor was provided by a magnetic stirrer and the reactorwas heated with a hot air gun. The glass reactor was operated in thebatch mode with acetic acid, cyclohexene, cyclooctane (internalstandard), and the catalyst loaded into the reactor before the reactorwas pressurized and heated to the desired operating condition. Thereactants and products were analyzed by gas chromatograph-massspectrometer.

[0135] The reaction was performed in excess of acetic acid (aceticacid/cyclohexene molar ratio of 5:1) to minimize the dimerization ofcyclohexene. Four different catalysts were tested at a temperature andpressure of 100° C. and 50 psig, respectively, for 5 hours time onstream. A blank run was also carried out under identical operatingconditions to determine whether the reaction proceeds in the absence ofany catalyst. Little or no cyclohexyl acetate was formed in the absenceof catalyst under the operating conditions mentioned above.

[0136] The four catalysts tested in this series of experiments includedsulfated zirconia, Amberlyst 15 (Rohm and Haas), “NAFION®” NR50(DuPont), and 13.5% “NAFION®” PFIEP/silica microcomposite material ofthe present invention (Example 13). The efficiency of the catalystsafter 5 hours time on stream were compared on the basis of specificactivity of the catalysts (measured as gmol of cyclohexylacetate/g-cat.hr) for the esterification reaction. The specific activityof the catalysts have been reported in Table II. TABLE II SpecificActivity × 10² (gmol cyclohexyl acetate) Catalyst (gm catalyst) · (hr)Sulfated Zirconia 16.8 Amberlyst 15 82.4 “NAFION ®” NR50 86.3 13.5%“NAFION ®” PFIEP/ 677.5 silica

[0137] Thus, the activity of 13.5 wt. % “NAFION®” PFIEP/silicamicrocomposite catalyst was found to be almost an order of magnitudehigher than that of Amberlyst 15 and “NAFION®” NR50 and approximately 40times higher than that of sulfated zirconia. The selectivity ofcyclohexyl acetate was greater than 90 mole % for Amberlyst 15,“NAFION®” NR50, and 13.5 wt. % “NAFION®” PFIEP/silica microcompositecatalysts while the selectivity was less than 50 mole % for sulfatedzirconia.

Example 44 Formation of “TERATHANE®” Using the “NAFION®” PFIEP/SilicaCatalyst

[0138] A 300 mL “TEFLON®” lined Parr pressure reactor equipped with amechanical agitator, an internal 420 micron filter, and a feed pump wasloaded with 9 g “NAFION®” PFIEP/silica catalyst of Example 18 and filledthe rest of the way with a solution comprising 27.9 parts 3-methyltetrahydrofuran, 71.1 parts tetrahydrofuran, 6 parts acetic anhydrideand 0.6 parts acetic acid. The reactor was assembled, air bled, andfeeds started such that the average contact time in the reactor was 10hrs. The reaction was conducted at ambient temperature. Polymer wasproduced at 5.9% conversion at 4000 Mn. More catalyst (34 g) was addedfor a total of 43 g, and the reaction continued. Polymer was produced at20% conversion and 3500 Mn.

[0139] No analysis of 3-methyl THF content of polymer was done. Thissystem of reactants with 9 g “NAFION®” NR50, 10 hr contact time wouldproduce 45-50% conversions.

Example 45 80% “NAFION®” PFIEP/20% Silica Composite

[0140] 40 g of TMOS, 7 g of water and 0.6 g of 0.04M HCl was stirred for15 mins. This was added to 1200 mL of a 5% “NAFION®” solution (which hadpreviously had 100 mL of 0.4M NaOH added over 5 mins. with stirring). Asoft gel was formed and the flask and contents were placed in an oven at95° C. under a nitrogen flow to dry. The hard glass-like product wasground and passed through a 10-mesh screen, and then the material wasstirred with 3.5M HCl for 1 h (with 500 mL of acid), followed by washingwith 500 mL of de-ionized water. The solid was collected by filtration.Acidification, washing and filtration were repeated a total of 5 times,and after the final wash the solid was dried under vacuum at 100° C. for24 h. Yield of dried product was 58 g.

Example 46 Organically Modified Silica/“NAFION®” PFIEP CompositeSiO₂/SiO_(3/2)Me/“NAFION®” PFIEP

[0141] 20 g of MeSi(OMe)₃ was mixed with 3 g of water and 0.3 g of 0.04MHCl. The solution was stirred for about 5 mins. A solution of 22 g ofTMOS, 3 g water and 0.3 g of 0.04M HCl (which was stirred for 3 mins.)was added to the MeSi-containing solution. The combined clear siliconcontaining solution was added to “NAFION®”/NaOH (60 mL of a 5% “NAFION®”solution which contains 30 mL of 0.4M NaOH added over 1 min.) and thesystem gelled in about 3-5 mins. The material was dried at 95° C. undera nitrogen flow. The hard glass-like product was ground and passedthrough a 10-mesh screen, and then the material was stirred with 3.5MHCl for 1 hour (with 100 mL of acid), followed by washing with 100 mL ofde-ionized water. The solid was collected by filtration. Acidification,washing and filtration were repeated a total of 5 times, and after thefinal wash the solid was dried under vacuum at 100° C. for 24 h. Yieldof dried product was about 20 g. The illustrative example as describedin Example 28 was carried out with the exception that 1 g of thematerial from this example was used in the catalysis run. The conversionwas found to be 44% of heptene.

Example 47 PhSiO_(3/2)/MeSiO_(3/2)/Me₂SiO/SiO₂/“NAFION®” PFIEP Composite

[0142] 5 g of PhSi(OMe)₃, 10 g MeSi(OMe)₃, 10 g Me₂Si(OMe)₂ were mixedand 4 g of water and 0.3 g of 0.04M HCl was added and stirred. To this22 g of TMOS which was stirred with 0.3 g of 0.04M HCl and 3 g of waterwas added and the silicon containing solution was stirred for 15 mins.To 40 g of the 5% “NAFION®” solution was added 25 ml of 0.4M NaOH over 1min. Next the silicon containing solution was added to the stirred“NAFION®” solution and the mixture was left to gel. The material wasdried at 95° C. under a nitrogen flow. The hard glass-like product wasground and passed through a 10-mesh screen, and then the material wasstirred with 3.5M HCl for 1 hour (with 100 mL of acid, which alsocontained 25 mL of ethanol to ensure wetting), followed by washing with100 mL of de-ionized water. The solid was collected by filtration.Acidification, washing and filtration were repeated a total of 5 times,and after the final wash the solid was dried under vacuum at 100° C. for24 h. The illustrative example as described in Example 28 was carriedout with the exception that 1 g of the material from this example wasused in the catalysis run. The conversion was found to be 48% ofheptene.

Example 48 Me₂SiO/SiO₂/“NAFION®” PFIEP Composite

[0143] 20 g Me₂Si(OMe)₂ were mixed and 3 g of water and 0.3 g of 0.04MHCl was added and stirred for 5 min. To this solution 25 g of TMOS whichwas stirred with 0.3 g of 0.04M HCl and 3.5 g of water was added, andthe silicon containing solution was stirred for 15 mins. To 50 g of the5% “NAFION®” solution was added 25 mL of 0.4M NaOH over 1 min. Next thesilicon containing solution was added to the stirred “NAFION®” solution,and the mixture was left to gel over about 30 seconds. The material wasdried at 95° C. under a nitrogen flow. The hard glass-like product wasground and passed through a 10-mesh screen, and then the material wasstirred with 3.5M HCl for 1 hour (with 100 mL of acid, which alsocontained 25 mL of ethanol to ensure wetting), followed by washing with100 mL of de-ionized water. The solid was collected by filtration.Acidification, washing and filtration were repeated a total of 5 timesand after the final wash the solid was dried under vacuum at 100° C. for24 h. The illustrative example as described in Example 28 was carriedout with the exception that 1 g of the material from this example wasused in the catalysis run. The conversion was found to be 37% ofheptene.

Example 49 Polydimethylsiloxane/Si/“NAFION®” PFIEP Composite

[0144] 8 g of polydimethylsiloxane was added to 25 g of TMOS which wasstirred with 0.3 g of 0.04M HCl and 3.5 g of water was added and thesilicon containing solution was stirred for 15 mins. To 50 g of the 5%“NAFION®” solution was added 25 mL of 0.4M NaOH over 1 min. Next thesilicon containing solution was added to the stirred “NAFION®” solution,and the mixture was left to gel over about 30 s. The material was driedat 95° C. under a nitrogen flow. The hard glass-like product was groundand passed through a 10-mesh screen, and then the material was stirredwith 3.5M HCl for 1 hour (with 100 mL of acid, which also contained 25mL of ethanol to ensure wetting), followed by washing with 100 mL ofde-ionized water. The solid was collected by filtration. Acidification,washing and filtration were repeated a total of 5 times, and after thefinal wash the solid was dried under vacuum at 100° C. for 24 h. Theillustrative example as described in Example 28 was carried out with theexception that 1 g of the material from this example was used in thecatalysis run. The conversion was found to be a 49% heptene.

Example 50 Comparative Example of “NAFION®” PFIEP Deposited upon aPre-Formed Support

[0145] Catalysis Study

[0146] A sample of “NAFION®” PFIEP deposited on top of a silica gelsupport was prepared according to the Illustrative Embodiment Ia of U.S.Pat. No. 4,038,213. The silica used was a porous silica (A Divisonsilica 62). The surface area was 300 m²/g which is the same as describedin U.S. Pat. No. 4,038,213, with a pore volume of 1.1 cc/gram. Theporous silica support was treated with an alcohol solution of “NAFION®”(5% “NAFION®” PFIEP), and the alcohol was removed on a rotary evaporatorleaving a 5% “NAFION®” on the silica catalyst. The support and “NAFION®”were dried at 150° C. before catalyst testing.

[0147] The illustrative example as described in Example 28 was carriedout with the exception that 2 g of the material from Example 50 was usedin the catalysis run. Thus, 2 g of a 5 wt. % “NAFION®” in silica wasused, which had a total of 0.1 g of catalyst. The conversion was foundto be 24% of heptene.

[0148] By comparison, when using the same “NAFION®” loading, using a“NAFION®” PFIEP/silica catalyst which had been made in situ (andconsisted of highly dispersed and entrapped “NAFION®” PFIEP) asdescribed, for example, in Examples 13-23 the conversion obtained wastypically 85-99%. Thus, when 1 g of the material from Example 21 wasused in the catalysis run (the the total weight of “NAFION®” PFIEP being0.1 g), the conversion was found to be 86% of heptene.

[0149] Microscopy Study

[0150] The microscopy was performed using a Hitachi S-5000SP microscope(a scanning electron microscope available from Hitachi Instruments,Japan) with a Norum EDS x-ray analysis. Particles, prepared according toExample 21, about 1-2 mm in size were mounted in an epoxy resin, whichwas set and the resin and particles were polished to give a polishedcross section of the particle, which reveals the interior of theparticle. Using EDS x-ray analysis in a spot mode (which analyzes asmall sub-micron area) showed the presence of Si, F, O and C all ofwhich were present across the whole interior part of the particle.Several areas within a particle and several different particles wereanalyzed and in all cases wherever Si was detected, F was also detectedshowing the intimate mixture of the two. No areas enriched in entirelySi or entirely F were observed. A uniform distribution of Si and F wasobserved.

[0151] Particles prepared according to the Illustrative Embodiment Ia ofU.S. Pat. No. 4,038,213 were in contrast non-uniform. In most of thesample where Si was detected, no measurable F was found. On the veryedge of the silica, a band of material rich in F was found but nosilica, representing a film of the “NAFION®” PFIEP on the outer edge ofthe silica particle, and not an intimate mixture of the “NAFION®” PFIEP.The film could be observed visibly and varied in thickness from about0.1 to 4-5 microns on a particle of about 100 microns which showed nofluorine within it. The film (on the outer silica surface) was alsoabsent in some areas. An intimate mixture of Si and was not observed.

[0152] Elemental x-ray maps (for Si, O and F) were prepared for theabove two samples. Using the procedure as described in Example 21, auniform distribution of all three elements was observed and was foundwithin the entire particle of the microcomposite of the presentinvention.

[0153] An x-ray elemental map of the sample as prepared according toU.S. Pat. No. 4,038,213, showed a film of the fluorocarbon at the outeredge of the silica, with the bulk of the material being only silica.

Example 51 Catalytic Testing of “NAFION®” PFIEP/Silica Composites Usingthe Alkylation of Diphenyl Ether with Dodecene Illustrative Example ofthe Present Invention

[0154] Both diphenyl ether and dodecene where dried over 3A molecularsieve before use (dried for 24 hours). In a round bottom flask was added17 g of diphenyl ether and 8.4 g of dodecene, and a “TEFLON®” coatedmagnetic stirrer added. A reflux condenser was attached to the flask anda slow stream of nitrogen passed over the top of the reflux condenser tominimize moisture. The flask and contents were heated to 150° C. Asample of 1 g of the “NAFION®” PFIEP/silica catalyst as described inExample 13 was dried in vacuum at 150° C. for 15 hours. The driedmaterial was added to the diphenyl ether and dodecene mixture and thesolution stirred and left to react for exactly 2 hours at 150° C. Aftertwo hours a sample was removed of the dodecene and was measured usinggas chromatography. In the GC analysis dodecane was used as a standard.The conversion of diphenyl ether was measured to be greater than 99%,leaving less than 1% of the dodecene unreacted.

Comparative Example

[0155] As a comparison experiment, the catalytic activity of 0.13 g of“NAFION®” NR50 was tested. 0.13 g represents the same weight of“NAFION®” PFIEP as tested above for the microcomposite. The exact sameprocedure was used, drying the NR50 at 150° C. for 16 hours and addingthe NR50 to the stirred solution of dodecene (8.4 g) and diphenyl ether(17 g) at 150° C. After 2 hour reaction time the conversion was found tobe about 5%, leaving 95% of the dodecene unreacted.

Example 52 60% “NAFION®” PFIEP in Silica

[0156] To 1200 g of a 5% “NAFION®” containing solution was added 150 gof 0.8M NaOH followed by 150 g of calcium carbonate powder. The flaskand contents were ultrasonicated for 2 minutes using a sonic horn.Separately to 135 g of tetraethoxysilane was added 37 ml of water and0.3 g of 3.5M HCl. The solution was stirred for 1 hour. The silicasolution was added to the “NAFION®” containing solution and the mixturewas left for 1 hour and then the material was dried in an oven at 95° C.for 2 days (with a stream of nitrogen purging through the oven),followed by drying in vacuum at 115° C. for 1 day. The solid was stirredwith 1 liter of 3.5M HCl overnight, followed by washing with 500 ml ofde-ionized water, and the solid collected by filtration. The solid wasfurther stirred with 500 ml of 3.5M HCl for 1 hour, filtered and washedwith 500 ml of de-ionized water and the process repeated a total of 5times. After the final wash the solid was dried under vacuum at 10⁰° C.for 24 h.

[0157] Acylation Reaction

[0158] Benzoyl chloride and m-xylene and were dried over a molecularsieve before use. In a round bottom flask was added 10.6 g of m-xyleneand 7 g of benzoyl chloride, and a “TEFLON®” coated magnetic stirreradded. A reflux condenser was attached to the flask and a slow stream ofnitrogen passed over the top of the reflux condenser to minimizemoisture. The flask and contents were heated to 130° C. A sample of 0.17gram of the “NAFION®” PFIEP/silica catalyst as described in this Examplewas dried in vacuum at 150° C. for 15 hours. The dried material wasadded to the m-xylene and benzoyl chloride mixture and the solutionstirred and left to react for exactly 6 hours at 130° C. After six hoursa sample was removed. In the GC analysis dodecane was used as astandard. The conversion of benzoyl chloride was found to be 75%.

Comparative Example

[0159] As a comparison experiment, the catalytic activity of 0.1 g of“NAFION®” NR50 PFIEP was tested. 0.1 g represents the same weight of“NAFION®” PFIEP as tested above for the composite. The exact sameprocedure was used, drying the “NAFIONet” NR50 PFIEP at 150° C. for 16hours and adding the “NAFION®” NR50 PFIEP to the stirred solution ofm-xylene and benzoyl chloride at 130° C. After 6 hour reaction time theconversion was found to be about 17%.

Example 53

[0160] The catalyst as prepared in Example 45 was used in this Examplefor catalytic testing of “NAFION®” PFIEP/silica composites using theacylation of m-xylene with benzoyl chloride.

[0161] The m-xylene and benzoyl chloride were dried over molecular sievebefore use. In a round bottom flask was added 10.6 g of m-xylene and 7 gof benzoyl chloride, and a “TEFLON®” coated magnetic stirrer added. Areflux condenser was attached to the flask and a slow stream of nitrogenpassed over the top of the reflux condenser to minimize moisture. Theflask and contents were heated to 130° C. The “NAFION®” PFIEP/silicacomposition (about 5 grams) was ground to a fine powder using amortar-and pestle over about 10 minutes. A sample of 0.125 gram of the“NAFION®” PFIEP/silica catalyst as described in Example 45 was dried invacuum at 150° C. for 15 hours. The dried material was added to them-xylene and benzoyl chloride mixture and the solution stirred and leftto react for exactly 6 hours at 130° C. After six hours a sample wasremoved. In the GC analysis dodecane was used as a standard. Theconversion of benzoyl chloride was found to be 90%, as compared to aconversion of 17% for the comparative example as described above in theComparative Example of 52.

Example 54 40% “NAFION®” PFIEP in Silica

[0162] To 1200 ml of “NAFION®” was added 150 ml of 1.2M NaOH over about10 minutes. Separately 204 g of tetramethoxysilane, 32.6 g of water and3 g of 0.04M HCl were mixed for 45 minutes and the silicon containingsolution was added to the “NAFION®” containing solution. The solutiongelled in about 1 minute and the flask and contents were placed in anoven at 100° C., with a nitrogen flow, for 2 days, followed by vacuumdrying for an additional day. The solid was ground and passed through a10 mesh screen and the solid was stirred with 3.5M HCl for 1 hour (with500 ml of acid), followed by washing with 500 ml of de-ionzied water,and the solid collected by filtration. This process was repeated a totalof 5 times and after the final wash the solid was dried under vacuum at100° C. for 24 h.

[0163] Acylation Reaction

[0164] The m-xylene and benzoyl chloride were dried over molecular sievebefore use. In a round bottom flask was added 10.6 g of m-xylene and 7 gof benzoyl chloride, and a “TEFLON®” coated magnetic stirrer added. Areflux condenser was attached to the flask and a slow stream of nitrogenpassed over the top of the reflux condenser to minimize moisture. Theflask and contents were heated to 130° C. A sample of 0.25 g of the“NAFION®” PFIEP/silica catalyst as described in this Example was driedin vacuum at 150° C. for 15 hours. The dried material was added to them-xylene and benzoyl chloride mixture and the solution stirred and leftto react for exactly 6 hours at 130° C. After six hours a sample wasremoved. In the GC analysis dodecane was used as a standard. Theconversion of benzoyl chloride was found to be 68% as compared to aconversion of 17% for the Comparative Example as described above in theComparative Example 52.

Example 55

[0165] To 350 ml of a 5% “NAFION®” containing solution was added 7.5 gof 8M NaOH. The solution was stirred for about 2 minutes. Separately, 12ml of water and 1 ml of 0.04M HCl were added to 75 g oftetramethoxysilane. The solution was stirred for 45 minutes, and thesilicon containing solution was added to the “NAFION®” solution. Thesystem gelled in about 10 seconds and the flask and contents were driedin an oven at 95° C. for 2 days followed by drying in vacuum at 117° C.for a further day. The solid was ground and passed through a 10-meshscreen, and then the material was stirred with 3.5M HCl for 1 hour (with250 ml of acid), followed by washing with 100 ml of de-ionized water,and the solid collected by filtration. This process was repeated a totalof times, and after the final wash (with 1000 ml of de-ionized water)the solid was dried under vacuum at 100° C. for 24 h.

Example 56

[0166] To 175 ml of a 5% “NAFION®” containing solution was added 2.5 gof 8M NaOH. The solution was stirred for about 2 minutes. Separately, 6ml of water and 0.6 ml of 0.04M HCl were added to 42 g oftetramethoxysilane. The solution was stirred for 5 minutes and thenadded to the “NAFION®” solution. The system gelled in about 10 secondsand the flask and contents were dried in an oven at 95° C. for 2 daysfollowed by drying in vacuum at 117° C. for a further day. The solid wasground and passed through a 10-mesh screen, and then the material wasstirred with 3.5M HCl for 1 hour (with 250 ml of acid), followed bywashing with 100 nil of de-ionized water, and the solid collected byfiltration. This process was repeated a total of 5 times, and after thefinal wash (with 1000 ml of de-ionized water) the solid was dried undervacuum at 100° C. for 24 h.

Example 57 1-Butene Isomerization in the Gas Phase

[0167] Solid acid catalyzed 1-butene isomerization to cis-2-butene,trans-2-butene and isobutene was carried out at temperatures between50-250° C. and ambient pressure in a ½″ stainless steel reactor. Thetested acid catalyst of the present invention was the 13 wt % “NAFION®”PFIEP/silica microcomposite prepared in Example 16 which was comparedwith “NAFION®” NR50 and “AMBERLYST 15®”. Typically, between 2.5-5.0 g ofcatalyst were loaded in the reactor. Prior to the reaction, catalystswere dried in vacuum oven at 150° C. for overnight except “AMBERLYST15®” was dried at 110° C. The reactant 1-butene was diluted with helium.The reaction mixture was analyzed by on-line gas chromatography (GC)equipped with a Flame Ionization Detector (FID) and a 25 m Plot columncoated with Al₂O₃/KCl.

[0168] The 1-butene isomerization results over the 2.5 g of the 13 wt %“NAFION®” PFIEP/silica microcomposite catalyst of the present inventionare listed in Table 1a and Table 1b below. Data in Table 1a show thatthe microcomposite prepared as in Example 16 is very efficient for thetitle reaction under mild conditions, even at 50° C., significant amountof 1-butene were converted to the 2-butenes. At 100° C., nearequilibrium n-butene distribution was obtained and extremely smallamounts of isobutene were formed. Isobutene as well as oligomers formedover the microcomposite catalyst were less than that produced from the“NAFION®” NR50 beads catalyst (see Table 2a below). TABLE 1A ProductDistribution for 1-Butene Isomerization over 2.5 g 13 wt % “NAFION ®”PFIEP/Silica Microcomposite Catalyst Under Ambient Pressure with FlowRate of He = 1-Butene = 38 ml/min, WHSV of 1-Butene = 2 hr⁻¹ Temperature(° C.) % Butenes 50 100 150 200 250 1-butene 38.0 15.8 15.3 21.2 25.0trans-2-butene 33.9 54.9 5.4 45.6 42.4 cis-2-butene 28.1 29.3 31.0 31.831.9 isobutene — — 0.3 0.4 0.7 Oligomers — — — ⁻2% ⁻5%

[0169] The reactant flow rate effect on the isomerziation over themicrocomposite was studied and the results are shown in Table 1b below.At 50° C., the thermodynamic equilibium distribution of n-butenes is4.1%, 70.5%, and 25.4% for 1-butene, trans-2-butene, and cis-2-butene,respectively. Data in Table 1b indicate that the equilibriumdistribution of n-butene can be readily obtained over the microcompositecatalyst at temperatures as low as 50° C. TABLE 1B Product Distributionfor 1-Butene Isomerization over 2.5 g 13 wt % “NAFION ®” PFIEP/SilicaComposite Catalyst Under Ambient Pressure at 50° C. and Different WHSVof 1-Butene with Flow Ratio of He/1-Butene = 2/1 WHSV (hr⁻¹) % Butenes0.4 0.8 1.6 1-butene 6.9 14.9 37.8 trans-2-butene 66.3 56.2 34.6cis-2-butene 26.8 28.9 27.6 isobutene — — —

[0170] Comparison with “NAFION®” NR50

[0171] Table 2a below lists the results from 1-butene isomerization overthe “NAFION®” NR50 beads at different temperatures. At 50° C. and theother reaction conditions listed in Table 2a, 1-butene conversion wasless than 1%. 1-Butene conversion increased gradually with increasedreaction temperature up to 200° C. The “NAFION®” NR50 beads melted at250° C. and resulted in decreased activity. At the temperature where“NAFION®” NR50 could effectively catalyze the 1-butene isomerization,about 200° C., significant amount of oligomers of butene (C₈+hydrocarbons) and the cracking products of those oligmers (C₁-C₇hydrocarbons) were also formed. In all cases, isobutene formation wasnegligible. TABLE 2A Product Distribtion for 1-Butene Isomerization over5.0 g “NAFION ®” NR50 Catalyst Under Ambient Pressure with Flow Rate ofHe = 1-butene = 38 ml/min, WHSV of 1-butene = 1 hr⁻¹ Temperature (° C.)% Butenes 50 100 150 200 250 1-butene >99.0 86.1 38.1 18.6 24.1trans-2-butene — 5.8 36.0 48.1 42.9 cis-2-butene <1.0 8.0 25.7 31.6 31.0isobutene — 0.1 0.2 1.7 3.0 Oligomers — — ⁻9% ⁻27% ⁻36%

[0172] The effect of reactant flow rate, that is the weight hourly spacevelocity (WHSV) of butene (hr⁻¹) was investigated and the resultobtained at 150° C. was listed in Table 2b below. As the flow rate wasdecreased, the contact times of the reactant with solid catalystincreased, and consequently the 1-butene conversion to 2-butenesincreased. However, the thermodynamic equilibrium distribution ofbutenes were not reached over the “NAFION®” NR50 catalyst under thereaction conditions employed. Only small changes of 1-butene wererealized when the same study was carried out at 100° C. and almost noeffect of WHSV on 1-butene conversion was seen at 50° C. TABLE 2BProduct Distribution for 1-Butene Isomerization over 5.0 g “NAFION ®”NR50 Catalyst Under Ambient Pressure at 150° C. and Different WHSV of1-Butene with Flow Ratio of He/1-Butene = 2/1 WHSV (hr⁻¹) % Butenes 0.20.4 0.8 1-butene 18.1 32.9 42.2 trans-2-butene 51.2 40.8 34.8cis-2-butene 30.2 26.0 23.0 isobutene 0.5 0.3 — Oligomers 25% 12% 9%

[0173] Comparison with “AMBERLYST 15®”

[0174] 1-Butene isomerization over commercial “AMBERLYST 15®” resincatalyst was also carried out under similar conditions for comparison.The temperature and flow rate effects are shown below in Table 3a andTable 3b, repectively. The highest temperature studied was 100° C.because the “AMBERLYST 15®” is known to decompose and lose sulfonicgroups at elevated temperatures (>130° C.). Data in Table 3a show thatthe macroporous “AMBERLYST 150” catalyst (surface area ⁻34 m²/g) is aneffective catalyst for the 1-butene isomerization to the linear2-butenes at the conditions employed and near equilibrium n-butenedistribution was obtained at 100° C. Similar to the results obtainedfrom the “NAFION®” NR50 and “NAFIONo” PFIEP/silica microcompositecatalysts, isobutene formation was negligible in all cases. TABLE 3AProduct Distribution for 1-Butene Isomerization over 5.0 g “AMBERLYST15 ®” Catalyst Under Ambient Pressure with Flow Rate of He = 110 ml/minand 1-Butene = 90 ml/min, WHSV of 1-Butene = 2.5 hr⁻¹ Temperature (° C.)% Butenes 50 75 100 1-butene 69.8 10.7 8.2 trans-2-butene 17.1 62.2 62.8cis-2-butene 13.1 27.1 28.8 isobutene — — 0.2 Oligomers — 1.5% 4.0%

[0175] Equilibrium was not reached at 50° C. even when very low flowrate of 1-butene was used (Table 3b). TABLE 3B Product Distribution for1-Butene Isomerization over 5.0 g “AMBERLYST 15 ®” Catalyst UnderAmbient Pressure at 50° C. and Different WHSV of 1-Butene with FlowRatio of He/1-Butene = 1.2/1.0 WHSV (hr − 1) % Butenes 0.28 0.44 1.032.08 2.50 1-butene 24.7 31.0 53.0 67.8 69.8 trans-2-butene 51.2 46.229.3 19.2 17.1 cis-2-butene 24.1 22.8 17.7 13.0 13.1 isobutene — — — — —

Example 58 1-Butene Isomerization in the Gas Phase

[0176] Solid acid catalyzed 1-butene isomerization to cis-2-butene,trans-2-butene and isobutene was carried out at temperatures between23-250° C. and ambient pressure with a ½″ stainless steel reactor. A 13wt % “NAFION®” PFIEP/silica microcomposite as prepared in Example 16 wasdried at 150° C. overnight. The reactant 1-butene was diluted withhelium. The reaction mixture was analyzed by an on-line GC equipped witha FID detector and a 25 m Plot column coated with Al₂O₃/KCl.

[0177] The 1-butene isomerization results over the 13 wt % “NAFION®”PFIEP/silica microcomposite catalyst are shown in Tables 4a and 4bbelow. FIG. 1 is a graph showing the data from Table 4b plotting thereciprocal of WHSV. TABLE 4A Product Distribution for 1-ButeneIsomerization over 5.0 g 13 wt % “NAFION ®” PFIEP/Silica MicrocompositeCatalyst Under Ambient Pressure with Flow Rate of He = 105 ml/min and1-Butene = 6 ml/min, WHSV of 1-Butene = 0.16 hr⁻¹ Temperature (° C.) %Butenes 50 100 150 200 250 1-butene 10.3 7.8 10.5 23.0 16.1trans-2-butene 62.4 63.2 57.9 54.6 50.8 cis-2-butene 27.3 28.6 29.9 29.931.2 isobutene — 0.1 0.4 1.1 1.5 Oligomers <1% 3% 3% 3% 3%

[0178] TABLE 4B Product Distribution for 1-Butene Isomerization over 5.0g 13 wt. % “NAFION ®” PFIEP/Silica Microcomposite Catalyst Under AmbientPressure at 50° C. and Different WHSV of 1-Butene with Flow Ratio ofHe/1-Butene = 1.21/1 WHSV (hr⁻¹) % Butenes 1.0 1.6 2.5 1-butene 6.6 8.89.2 trans-2-butene 66.9 64.0 63.6 cis-2-butene 26.5 27.2 27.2 isobutene— — —

Example 59 1-Heptene Isomerization in the Liquid Phase

[0179] Solid acid catalyzed 1-heptene isomerization to 2- and 3-heptenes(including cis- and trans-isomers of each) were carried out in theliquid phase at 60° C. Typically, 10 g of 1-heptene, 30 g of n-hexaneand 2 g of solid catalyst which was predried were charged to a two-neckflask with a magnetic stir bar for mixing. n-Hexane served as solventfor the reaction and internal standard for the GC analysis. Liquidsamples were taken at certain time intervals and analyzed by the GC thatwas described earlier. All of the five isomers were separated andidentified. Good material balances were obtained and formation ofoligomers was negligible. The 1-heptene conversions after 1 hr at 60° C.and the first order rate constants that were calculated from the data atlow 1-heptene conversions (<15%) are listed in Table 5 below. Similar tothe gas phase 1-butene isomerization, the 13 wt % “NAFION®” PFIEP/silicamicrocomposite as prepared in Example 16 was significantly more activethan the “NAFION®” NR50 beads and also was about 6 times more activethan the “AMBERLYST 15®” catalyst based on the unit weight of the solidcatalyst. TABLE 5 1-Heptene Conversion (mol %) after 1 hr at 60° C. andthe First Order Rate Constant for 1-Heptene Isomerization over 2 g ofSolid Acid Catalysts 13 wt % “NAFION ®” PFIEP/Silica Micro- “NAFION ®”Catalyst composite NR50 “AMBERLYST 15 ®” 1-Heptene 86.4 3.8 20.6 Conv.(%) Rate Constant 86.8 2.0 13.7 (mM/gcat · hr)

Example 60 1-Dodecene Isomerization in the Liquid Phase

[0180] 1-Dodecene isomerization to its isomers was carried out in theliquid phase at 75° C. over 13 wt % “NAFION®” PFIEP/silicamicrocomposite as prepared in Example 16 and compared with “NAFION®”NR50 and “AMBERLYST 152” catalysts. For a typical run, 10 g of1-dodecene, 30 g of cyclohexane and 2 g of solid catalyst which waspredried were charged to a two-neck flask with a magnetic stir bar formixing. Cyclohexane served as solvent for the reaction and internalstandard for the GC analysis. Liquid samples were taken at certain timeintervals and analyzed by the GC that was described earlier. There wasno attempt to identify all of the n-dodecene isomers and only the1-dodecene conversion was monitored by following the decreasing of itsGC peak area. Formation of oligomers was negligible. The 1-dodeceneconversions after 1 hr at 75° C. and the first order rate constants thatwere calculated from the data at low 1-dodecene conversions (<15%) werelisted in Table 6 below. Similar to the gas phase 1-butene isomerizationand the liquid phase 1-heptene isomerization, the 13 wt % “NAFION®”PFIEP/silica microcomposite was the most active catalyst which was about20 times more active than the “NAFION®” NR50 beads and was also about 4times more active than the “AMBERLYST 15®” catalyst based on the unitweight of the solid catlayst. TABLE 6 1-Dodecene Conversion (mol %)After 1 hr at 75° C. and the First Order Rate Constant for 1-DodeceneIsomerization over 2 g of Solid Acid Catalysts 13 wt % “NAFION ®”PFIEP/Silica Micro- “NAFION ®” Catalyst composite NR50 “AMBERLYST 15 ®”1-Dodecene 76.6 13.6 57.7 Conv. (%) Rate Constant 192.5 9.2 52.2(mM/gcat · hr)

What is claimed is:
 1. A porous microcomposite comprising perfluorinatedion-exchange polymer with pendant sulfonic and/or carboxylic acid groupsentrapped within and highly dispersed throughout a network of metaloxide, wherein the weight percentage of perfluorinated ion-exchangepolymer in the microcomposite is from about 0.1 to about 90 percent,wherein the size of the pores in the microcomposite is about 0.5 nm toabout 75 nm, and wherein the microcomposite optionally further comprisespores having a size in the range of about 75 nm to about 1000 nm.
 2. Themicrocomposite of claim 1 wherein the perfluorinated ion-exchangepolymer contains pendant sulfonic acid groups.
 3. The microcomposite ofclaim 1 wherein the metal oxide is silica, alumina, titania, germania,zirconia, alumino-silicate, zirconyl-silicate, chromic oxide and/or ironoxide.
 4. The microcomposite of claim 1 wherein the metal oxide issilica.
 5. The microcomposite of claim 4 wherein the perfluoroinatedion-exchange polymer is prepared from resin having an equivalent weightof about 1070 comprising about 6.3 tetrafluoroethylene molecules forevery perfluoro(3,6-dioxa-4-methyl-7-octenesulfonyl fluoride) molecule,and the weight percent of perfluorinated ion-exchange polymer is about13%.
 6. The microcomposite of claim 1 wherein the weight percentage ofperfluorinated ion-exchange polymer is from about 5 to about
 80. 7. Themicrocomposite of claim 1 wherein the size of the pores is about 0.5 nmto about 30 nm.
 8. The microcomposite of claim 1 wherein saidmicrocomposite further comprises pores having a size in the range ofabout 75 nm to about 1000 nm.
 9. The microcomposite of claim 8 whereinthe perfluorinated ion-exchange polymer contains pendant sulfonic acidgroups, and wherein the metal oxide is silica.
 10. The process ofpreparation of a porous microcomposite which comprises perfluorinatedion-exchange polymer containing pendant sulfonic and/or carboxylic acidgroups entrapped within and highly dispersed throughout a network ofmetal oxide, wherein the weight percentage of perfluorinatedion-exchange polymer in the microcomposite is from about 0.1 to about 90percent, wherein the size of the pores in the microcomposite is about0.5 nm to about 75 nm, and wherein the microcomposite optionally furthercomprises pores having a size in the range of about 75 nm to about 1000nm; said process comprising the steps of: a. mixing the perfluorinatedion-exchange polymer with one or more metal oxide precursors in a commonsolvent; b. initiating gelation; c. allowing sufficient time forgelation and aging of the mixture; and d. removing the solvent.
 11. Theprocess of claim 10 further comprising the steps, after d: e. acidifyingthe product of step d by addition of an acid; and f. removing the excessacid.
 12. The process of claim 11 further comprising at step a, addingto the mixture an amount from about 1 to 80 weight percent of an acidextractable filler particle, whereby said microcomposite furthercontains pores having a size in the range of about 75 nm to about 1000nm.
 13. The process of claim 12 wherein the acid extractable fillerparticle is calcium carbonate.
 14. The process of claim 10 wherein theperfluorinated ion-exchange polymer contains pendant sulfonic acidgroups.
 15. The process of claim 10 wherein the metal oxide is silica.16. The process of claim 11 further comprising after step d and beforestep e: grinding the product of step d.
 17. An improved process for thenitration of an aromatic compound wherein the improvement comprisescontacting said aromatic compound with a catalytic porous microcompositecomprising perfluorinated ion-exchange polymer with pendant sulfonicand/or carboxylic acid groups entrapped within and highly dispersedthroughout a network of metal oxide, wherein the weight percentage ofperfluorinated ion-exchange polymer in the microcomposite is from about0.1 to about 90 percent, wherein the size of the pores in themicrocomposite is about 0.5 nm to about 75 nm, and wherein themicrocomposite optionally further comprises pores having a size in therange of about 75 nm to about 1000 nm.
 18. The process of claim 17wherein the aromatic compound is benzene.
 19. The process of claim 17wherein the perfluorinated ion-exchange polymer contains pendantsulfonic acid groups and the metal oxide is silica, alumina, titania,germania, zirconia, alumino-silicate, zirconyl-silicate, chromic oxideand/or iron oxide.
 20. The process of claim 19 wherein the metal oxideis silica and said microcomposite further comprises pores having a sizein the range of about 75 nm to about 1000 nm.
 21. An improved processfor the esterification of a carboxylic acid with an olefin wherein theimprovement comprises contacting said carboxylic acid with a catalyticporous microcomposite comprising perfluorinated ion-exchange polymerwith pendant sulfonic and/or carboxylic acid groups entrapped within andhighly dispersed throughout a network of metal oxide, wherein the weightpercentage of perfluorinated ion-exchange polymer in the microcompositeis from about 0.1 to about 90 percent, wherein the size of the pores inthe microcomposite is about 0.5 nm to about 75 nm, and wherein themicrocomposite optionally further comprises pores having a size in therange of about 75 nm to about 1000 nm.
 22. The process of claim 21wherein the carboxylic acid is acetic acid and the olefin iscyclohexene.
 23. The process of claim 21 wherein the perfluorinatedion-exchange polymer contains pendant sulfonic acid groups and the metaloxide is silica, alumina, titania, germania, zirconia, alumino-silicate,zirconyl-silicate, chromic oxide and/or iron oxide.
 24. The process ofclaim 23 wherein the metal oxide is silica and said microcompositefurther comprises pores having a size in the range of about 75 nm toabout 1000 nm.
 25. A process for regenerating a catalyst comprisingperfluorinated ion-exchange polymer with pendant sulfonic and/orcarboxylic acid groups entrapped within and highly dispersed throughouta network of metal oxide, wherein the weight percentage ofperfluorinated ion-exchange polymer in the microcomposite is from about0.1 to about 90 percent, wherein the size of the pores in themicrocomposite is about 1 nm to about 75 nm, and wherein themicrocomposite optionally further comprises pores having a size in therange of about 75 nm to about 1000 nm, comprising the steps of: (a)contacting the microcomposite with an acid; and (b) removing the excessacid to yield the regenerated catalyst.
 26. The process of claim 25wherein the perfluorinated ion-exchange polymer contains pendantsulfonic acid groups and the metal oxide is silica, alumina, titania,germania, zirconia, alumino-silicate, zirconyl-silicate, chromic oxideand/or iron oxide.
 27. The process of claim 26 wherein the metal oxideis silica and said microcomposite further comprises pores having a sizein the range of about 75 nm to about 1000 nm.
 28. An improved processfor the dimerization of an alpha substituted styrene wherein theimprovement comprises contacting said alpha substituted sytrene with acatalytic porous microcomposite comprising perfluorinated ion-exchangepolymer with pendant sulfonic and/or carboxylic acid groups entrappedwithin and highly dispersed throughout a network of metal oxide, whereinthe weight percentage of perfluorinated ion-exchange polymer in themicrocomposite is from about 0.1 to about 90 percent, wherein the sizeof the pores in the microcomposite is about 1 nm to about 75 nm, andwherein the microcomposite optionally further comprises pores having asize in the range of about 75 nm to about 1000 nm.
 29. The process ofclaim 28 wherein the alpha substituted styrene is alpha methyl styrene.30. The process of claim 28 wherein the perfluorinated ion-exchangepolymer contains pendant sulfonic acid groups and the metal oxide issilica, alumina, titania, germania, zirconia, alumino-silicate,zirconyl-silicate, chromic oxide and/or iron oxide.
 31. The process ofclaim 30 wherein the metal oxide is silica and said microcompositefurther comprises pores having a size in the range of about 75 nm toabout 1000 nm.
 32. An improved process for the alkylation of an aromaticcompound with an olefin wherein the improvement comprises contactingsaid aromatic compound with a catalytic porous microcomposite comprisingperfluorinated ion-exchange polymer with pendant sulfonic and/orcarboxylic acid groups entrapped within and highly dispersed throughouta network of metal oxide, wherein the weight percentage ofperfluorinated ion-exchange polymer in the microcomposite is from about0.1 to about 90 percent, wherein the size of the pores in themicrocomposite is about 1 nm to about 75 nm, and wherein themicrocomposite optionally further comprises pores having a size in therange of about 75 nm to about 1000 nm.
 33. The process of claim 32wherein the perfluorinated ion-exchange polymer contains pendantsulfonic acid groups and the metal oxide is silica, alumina, titania,germania, zirconia, alumino-silicate, zirconyl-silicate, chromic oxideand/or iron oxide.
 34. The process of claim 33 wherein the metal oxideis silica and said microcomposite further comprises pores having a sizein the range of about 75 nm to about 1000 nm.
 35. An improved processfor the polymerization of tetrahydrofuran to polytetramethylene etheracetate wherein the improvement comprises contacting saidtetrahydrofuran with a catalytic porous microcomposite comprisingperfluorinated ion-exchange polymer with pendant sulfonic and/orcarboxylic acid groups entrapped within and highly dispersed throughouta network of metal oxide, wherein the weight percentage ofperfluorinated ion-exchange polymer in the microcomposite is from about0.1 to about 90 percent, wherein the size of the pores in themicrocomposite is about 0.5 nm to about 75 nm, and wherein themicrocomposite optionally further comprises pores having a size in therange of about 75 nm to about 1000 nm.
 36. The process of claim 35wherein the perfluorinated ion-exchange polymer contains pendantsulfonic acid groups and the metal oxide is silica, alumina, titania,germania, zirconia, alumino-silicate, zirconyl-silicate, chromic oxideand/or iron oxide.
 37. The process of claim 36 wherein the metal oxideis silica and said microcomposite further comprises pores having a sizein the range of about 75 nm to about 1000 nm.
 38. An improved processfor the acylation of an aromatic compound with an acyl halide whereinthe improvement comprises contacting said aromatic compound with acatalytic porous microcomposite comprising perfluorinated ion-exchangepolymer with pendant sulfonic and/or carboxylic acid groups entrappedwithin and highly dispersed throughout a network of metal oxide, whereinthe weight percentage of perfluorinated ion-exchange polymer in themicrocomposite is from about 0.1 to about 90 percent, wherein the sizeof the pores in the microcomposite is about 0.5 nm to about 75 nm, andwherein the microcomposite optionally further comprises pores having asize in the range of about 75 nm to about 1000 nm.
 39. The process ofclaim 38 wherein the aromatic compound is m-xylene and the acyl halideis benzoyl chloride.
 40. The process of claim 38 wherein theperfluorinated ion-exchange polymer contains pendant sulfonic acidgroups and the metal oxide is silica, alumina, titania, germania,zirconia, alumino-silicate, zirconyl-silicate, chromic oxide and/or ironoxide.
 41. The process of claim 40 wherein the metal oxide is silica andsaid microcomposite further comprises pores having a size in the rangeof about 75 nm to about 1000 nm.
 42. A process for the isomerization ofan olefin, comprising contacting said olefin at isomerization conditionswith a catalytic amount of a porous microcomposite, said microcompositecomprising a perfluorinated ion-exchange polymer with pendant sulfonicand/or carboxylic acid groups entrapped within and highly dispersedthroughout a network of metal oxide, wherein the weight percentage ofperfluorinated ion-exchange polymer in the microcomposite is from about0.1 to about 90 percent, wherein the size of the pores in themicrocomposite is about 0.5 nm to about 75 nm, and wherein themicrocomposite optionally further comprises pores having a size in therange of about 75 nm to about 1000 nm.
 43. The process of claim 42wherein the isomerization conditions comprise a temperature of fromabout 0° C. to about 300° C., a pressure of from about atmospheric to100 atmospheres, and a weight hourly space velocity of from about 0.1 to100 hr⁻¹.
 44. The process of claim 43 wherein the isomerizationconditions comprise a temperature of from about 25° C. to about 250° C.,a pressure of from about atmospheric to 50 atmospheres, and a weighthourly space velocity of from about 0.1 to 10 hr⁻¹.
 45. The process ofclaim 42 wherein the perfluorinated ion-exchange polymer containspendant sulfonic acid groups.
 46. The process of claim 42 wherein themetal oxide is silica, alumina, titania, germania, zirconia,alumino-silicate, zirconyl-silicate, chromic oxide and/or iron oxide.47. The process of claim 45 wherein the metal oxide is silica.
 48. Theprocess of claim 42 wherein the weight percentage of perfluorinatedion-exchange polymer is from about 5 to about
 80. 49. The process ofclaim 48 wherein the weight percentage of perfluorinated ion-exchangepolymer is from about 5 to about
 20. 50. The process of claim 42 whereinthe size of the pores is about 0.5 nm to about 30 nm.
 51. The process ofclaim 42 wherein said microcomposite further comprises pores having asize in the range of about 75 nm to about 1000 nm.
 52. The process ofclaim 42 wherein the olefin is a C₄ to C₄₀ primary olefin.
 53. Theprocess of claim 52 wherein the olefin is 1-butene, 1-heptene or1-dodecene.
 54. The process of claim 53 wherein the olefin is 1-butene.55. The process of claim 53 wherein the weight percentage ofperfluorinated ion-exchange polymer is from about 5 to about 80, theperfluorinated ion-exchange polymer contains pendant sulfonic acidgroups, and the metal oxide is silica.
 56. The process of claim 53wherein the perfluorinated ion-exchange polymer is prepared from resinhaving an equivalent weight of about 1070 comprising about 6.3tetrafluoroethylene molecules for every perfluoro(3,6-dioxa-4-methyl-7-octenesulfonyl fluoride) molecule, and the weightpercent of perfluorinated ion-exchange polymer is about 13%.